Ultrapure synthetic carbon materials

ABSTRACT

The present application is generally directed to ultrapure synthetic carbon materials having both high surface area and high porosity, ultrapure polymer gels and devices containing the same. The disclosed ultrapure synthetic carbon materials find utility in any number of devices, for example, in electric double layer capacitance devices and batteries. Methods for making ultrapure synthetic carbon materials and ultrapure polymer gels are also disclosed.

CROSS-REFERENCES TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. §119(e) ofU.S. Provisional Patent Application No. 61/222,431 filed on Jul. 1,2009; U.S. Provisional Patent Application No. 61/255,037 filed on Oct.26, 2009; U.S. Provisional Patent Application No. 61/255,054 filed onOct. 26, 2009; and U.S. Provisional Patent Application No. 61/261,703filed on Nov. 16, 2009; all of which are incorporated herein byreference in their entireties.

STATEMENT OF GOVERNMENT INTEREST

Partial funding of the work described herein was provided by the U.S.Government under Contract No. W15P7T-09-C-S311 provided by theDepartment of Defense. The U.S. Government may have certain rights inthis invention.

BACKGROUND

1. Technical Field

The present invention generally relates to ultrapure synthetic carbonmaterials, methods for making the same and devices containing the same.

2. Description of the Related Art

Activated carbon is commonly employed in electrical storage anddistribution devices. The high surface area, conductivity and porosityof activated carbon allows for the design of electrical devices havinghigher energy density than devices employing other materials. Electricdouble-layer capacitors (EDLCs) are an example of such devices. EDLCsoften have electrodes prepared from an activated carbon material and asuitable electrolyte, and have an extremely high energy density comparedto more common capacitors. Typical uses for EDLCs include energy storageand distribution in devices requiring short bursts of power for datatransmissions, or peak-power functions such as wireless modems, mobilephones, digital cameras and other hand-held electronic devices. EDLCsare also commonly use in electrice vehicles such as electric cars,trains, buses and the like.

Batteries are another common energy storage and distribution devicewhich often contain an activated carbon material (e.g., as anodematerial, current collector, or conductivity enhancer). For example,lithium/carbon batteries having a carbonaceous anode intercalated withlithium represent a promising energy storage device. Other types ofcarbon-containing batteries include lithium air batteries, which useporous carbon as the current collector for the air electrode, and leadacid batteries which often include carbon additives in either the anodeor cathode. Batteries are employed in any number of electronic devicesrequiring low current density electrical power (as compared to an EDLC'shigh current density).

One known limitation of EDLCs and carbon-based batteries is decreasedperformance at high-temperature, high voltage operation, repeatedcharge/discharge cycles and/or upon aging. This decreased performancehas been attributed to electrolyte impurity or impurities in the carbonelectrode itself, causing breakdown of the electrode at theelectrolyte/electrode interface. Thus, it has been suggested that EDLCsand/or batteries comprising electrodes prepared from higher puritycarbon materials could be operated at higher voltages and for longerperiods of time at higher temperatures than existing devices.

Although the need for higher purity carbon materials having both highsurface area and high porosity has been recognized, such carbon materialis not commercially available and no reported preparation method iscapable of yielding the high purity carbon desired for high performanceelectrical devices. One common method for producing high surface areaactivated carbon materials is to pyrolyze an existing carbon-containingmaterial (e.g., coconut fibers or tire rubber). This results in a charwith relatively low surface area which can subsequently beover-activated to produce a material with the surface area and porositynecessary for the desired application. Such an approach is inherentlylimited by the existing structure of the precursor material, andtypically results in low process yields and a carbon material having anash content (i.e., metal impurities) of 1% or higher.

Activated carbon materials can also be prepared by chemical activation.For example, treatment of a carbon-containing material with an acid,base or salt (e.g., phosphoric acid, potassium hydroxide, sodiumhydroxide, zinc chloride, etc.) followed by heating results in anactivated carbon material. However, such chemical activation producesactivated carbon materials with a high level of residual processimpurities (e.g., metals).

Another approach for producing high surface area activated carbonmaterials is to prepare a synthetic polymer from carbon-containingorganic building blocks (e.g., a ultrapure polymer gel). As with theexisting organic materials, the synthetically prepared polymers arepyrolyzed and activated to produce an activated carbon material. Incontrast to the traditional approach described above, the intrinsicporosity of the synthetically prepared polymer results in higher processyields because less material is lost during the activation step.However, as with carbon materials prepared from other known methods,activated carbon materials prepared from synthetic polymers via reportedmethods contain unsuitable levels of impurities (e.g., metals).

While significant advances have been made in the field, there continuesto be a need in the art for highly pure carbon materials, as well as formethods of making the same and devices containing the same. The presentinvention fulfills these needs and provides further related advantages.

BRIEF SUMMARY

In general terms, the present invention is directed to ultrapuresynthetic carbon materials, as well as to methods for making suchmaterials and to devices containing the same. Such materials findapplication in the context of electrical storage and distributiondevices, particularly for use in electrodes for EDLCs and batteries.Existing carbon materials contain residual levels of various impurities(e.g., chlorine, sulfur, metals, etc.) which are known to decrease thebreakdown voltage of the electrolyte in which the electrodes areimmersed. Thus, existing electrodes must be operated at lower voltagesand have a shorter life span than devices comprising the ultrapuresynthetic carbon materials of this invention. The impurities in carbonelectrodes also contribute to degradation of other components within anEDLC or battery. For example the porous membrane which separates the twocarbon electrodes in an EDLC may be degraded by chlorine or otherimpurities within the carbon electrode. The ultrapure synthetic carbonmaterials disclosed herein are significantly more pure than any knowncarbon materials and thus improve the operation of any number ofelectrical storage and/or distribution devices

Accordingly, in one embodiment, an ultrapure synthetic carbon materialis disclosed. The ultrapure synthetic carbon material comprises a totalimpurity content of less than 500 ppm of elements having atomic numbersranging from 11 to 92 as measured by proton induced x-ray emission. Inanother embodiment of the foregoing, the carbon material is an ultrapuresynthetic amorphous carbon material.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises a total impuritycontent of less than 200 ppm of elements having atomic numbers rangingfrom 11 to 92 as measured by proton induced x-ray emission.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises an ash contentof less than 0.03%, for example less than 0.01%, as calculated fromproton induced x-ray emission data.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises at least 95%carbon by weight as measured by combustion analysis and proton inducedx-ray emission.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises less than 3 ppmiron, less than 1 ppm nickel, less than 5 ppm sulfur, less than 1 ppmchromium or less than 1 ppm copper as measured by proton induced x-rayemission.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises less than 100ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc as measured by proton induced x-ray emission. For example, in someembodiments, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises less than 50 ppm sodium,less than 50 ppm silicon, less than 30 ppm sulfur, less than 10 ppmcalcium, less than 2 ppm iron, less than 1 ppm nickel, less than 1 ppmcopper, less than 1 ppm chromium and less than 1 ppm zinc as measured byproton induced x-ray emission.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises less than 3.0%oxygen, less than 0.1% nitrogen and less than 0.5% hydrogen asdetermined by combustion analysis. For example, in other specificembodiments, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises less than 1.0% oxygen asdetermined by combustion analysis.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises a pyrolyzedultrapure polymer cryogel. While in other embodiments, the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises an activated ultrapure polymer cryogel.

In some other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises a BET specificsurface area of at least 1500 m²/g, at least 2000 m²/g or at least 2400m²/g.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises a pore volume ofat least 0.7 cc/g.

In another embodiment, an ultrapure polymer gel is provided. Theultrapure polymer gel comprises carbon, hydrogen, oxygen and a totalimpurity content of less than 500 ppm, and typically less than 200 ppm,of elements having atomic numbers ranging from 11 to 92 as measured byproton induced x-ray emission.

In some embodiments, the ultrapure polymer gel is a dried ultrapurepolymer gel. In another embodiment, the ultrapure polymer gel comprisesa BET specific surface area of at least 400 m²/g.

In some other embodiments, the ultrapure polymer gel is prepared byadmixing one or more miscible solvents, one or more phenolic compounds,one or more aldehydes and one or more catalysts. For example, in someembodiments, the ultrapure polymer gel is prepared by admixing water,acetic acid, resorcinol, formaldehyde and ammonium acetate.

This high purity of the disclosed carbon materials can be attributed tothe disclosed sol gel process. Applicants have discovered that when oneor more polymer precursors, for example a phenolic compound and analdehyde, are co-polymerized under acidic conditions in the presence ofa volatile basic catalyst, an ultrapure polymer gel results. This is incontrast to other reported methods for the preparation of ultrapurepolymer gels which result in ultrapure polymer gels comprising residuallevels of metals and/or other impurities as well as residual levels ofreaction solvent and/or extraction solvent. Preparation of carbonmaterials from these impure ultrapure polymer gels, for example bypyrolysis and/or activation, results in carbon materials which are alsoimpure.

The disclosed ultrapure synthetic amorphous carbon material may be madefrom the ultrapure polymer gel by pyrolysis and/or activation of theultrapure polymer gel The ultrapure polymer gel, in turn, may be made byreacting one or more polymer precursors under acidic conditions in thepresence of a volatile basic catalyst to obtain a ultrapure polymer gel.

Accordingly, in one embodiment the present disclosure provides a methodfor making an ultrapure synthetic carbon material, the method comprisingreacting one or more polymer precursors under acidic conditions in thepresence of a volatile basic catalyst to obtain an ultrapure polymergel. In a further embodiment, the carbon material is an ultrapuresynthetic amorphous carbon material.

In other embodiments, the method further comprises admixing the one ormore polymer precursors in a solvent comprising acetic acid and water.In other embodiments, the volatile basic catalyst comprises ammoniumcarbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide,or combinations thereof, and in other embodiments the one or morepolymer precursors comprise resorcinol and formaldehyde.

In some other embodiments, the method further comprises:

-   -   (a) freeze drying the ultrapure polymer gel to obtain an        ultrapure polymer cryogel;    -   (b) pyrolyzing the ultrapure polymer cryogel to obtain a        pyrolyzed ultrapure cryogel; and    -   (c) activating the pyrolyzed ultrapure cryogel to obtain        ultrapure synthetic activated carbon material.

The ultrapure synthetic amorphous carbon material finds utility in anynumber of electrical storage and distribution devices. The combinationof ultrapurity, high porosity and high surface area allows for thepreparation of electrical storage and distribution devices havingproperties superior to known devices. The devices comprising theultrapure synthetic amorphous carbon material are capable of operationat higher voltages for longer periods of time at higher temperaturesthan comparable devices prepared from lower purity carbon.

Accordingly, in another embodiment the present disclosure provides adevice comprising an ultrapure synthetic carbon material, wherein theultrapure synthetic carbon material comprises a total impurity contentof less than 500 ppm, particularly 200 ppm, of elements having atomicnumbers ranging from 11 to 92 as measured by proton induced x-rayemission. For example, in some other embodiments of the foregoing thecarbon material is an ultrapure synthetic amorphous carbon material.

In some further embodiments the device is an electric double layercapacitor (EDLC) device comprising:

-   -   a) a positive electrode and a negative electrode wherein each of        the positive and the negative electrodes comprise the ultrapure        synthetic carbon material;    -   b) an inert porous separator; and    -   c) an electrolyte;    -   wherein the positive electrode and the negative electrode are        separated by the inert porous separator.

In some further embodiments, the EDLC device comprises a gravimetricpower of at least 15 W/g, a volumetric power of at least 10 W/cc, agravimetric energy of at least 20.0 Wh/kg or a volumetric energy of atleast 10.0 Wh/liter.

In some other embodiments, the EDLC device comprises a gravimetriccapacitance of at least of at least 25 F/g or a volumetric capacitanceof at least of at least 20 F/cc as measured by constant currentdischarge from 2.7 V to 0.1 V with a 5 second time constant employing a1.8 M solution of tetraethylammonium-tetrafluororoborate in acetonitrileelectrolyte and a current density of 0.5 A/g.

In some other further embodiments of the EDLC device, the ash content ofthe carbon material is less than 0.03%, particularly less than 0.01%, ascalculated from proton induced x-ray emission data, and in some otherembodiments the carbon material comprises at least 95% carbon asmeasured by combustion analysis and proton induced x-ray emission.

In some other embodiments of the EDLC device, the carbon materialcomprises less than 3 ppm iron, less than 1 ppm nickel, less than 5 ppmsulfur, less than 1 ppm chromium or less than 1 ppm copper as measuredby proton induced x-ray emission.

In yet other embodiments of the EDLC device, the carbon materialcomprises less than 100 ppm sodium, less than 300 ppm silicon, less than100 ppm calcium, less than 50 ppm sulfur, less than 20 ppm iron, lessthan 10 ppm nickel, less than 140 ppm copper, less than 5 ppm chromiumand less than 5 ppm zinc as measured by proton induced x-ray emission.

In some other embodiments of the EDLC device, the carbon materialcomprises an activated ultrapure polymer cryogel, and in some otherembodiments of the EDLC device the carbon material comprises a BETspecific surface area of at least 1500 m²/g, at least 2000 m²/g or atleast 2400 m²/g.

In other particular embodiments, the present disclosure is directed to abattery, for example a lithium/carbon battery, zinc/carbon battery,lithium air battery or lead acid battery, comprising an ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial as disclosed herein. In other embodiments, the presentdisclosure is directed to an electrode comprising an ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material asdisclosed herein. Such electrodes are useful in electrical storage anddistribution devices, such as EDLCs and batteries.

BRIEF DESCRIPTION OF THE DRAWINGS

In the figures, identical reference numbers identify similar elements.The sizes and relative positions of elements in the figures are notnecessarily drawn to scale and some of these elements are arbitrarilyenlarged and positioned to improve figure legibility. Further, theparticular shapes of the elements as drawn are not intended to conveyany information regarding the actual shape of the particular elements,and have been solely selected for ease of recognition in the figures.

FIG. 1 shows incremental pore volume vs. pore width for RF ultrapurepolymer cryogels produced from 100% acetic acid solvent.

FIG. 2 depicts incremental pore volume vs. pore width for RF ultrapurepolymer cryogels produced from 90:10 acetic acid:water solvent.

FIG. 3 depicts incremental pore volume vs. pore width for RF ultrapurepolymer cryogels produced from 50:50 acetic acid:water solvent.

FIG. 4 presents incremental pore volume vs. pore width for RF ultrapurepolymer cryogels produced from 25:75 acetic acid:water solvent.

FIG. 5 presents incremental pore volume vs. pore width for RF ultrapurepolymer cryogels produced from 10:90 acetic acid:water solvent.

FIG. 6 is a plot of specific surface area vs. pH for RF ultrapurepolymer cryogels produced from RS=0.3 and varying levels of acetic acidand ammonium salts.

FIGS. 7A and 7B are plots of incremental pore volume of a RF ultrapurepolymer cryogel and a pyrolyzed RF ultrapure polymer cryogel,respectively.

FIGS. 8A and 8B are plots of incremental pore volume of a RF ultrapurepolymer cryogel and a pyrolyzed RF ultrapure polymer cryogel,respectively.

FIGS. 9A and 9B are plots of incremental pore volume of a RF ultrapurepolymer cryogel and a pyrolyzed RF ultrapure polymer cryogel,respectively.

FIGS. 10A and 10B are plots of incremental pore volume of a RF ultrapurepolymer cryogel and a pyrolyzed RF ultrapure polymer cryogel,respectively.

FIGS. 11A and 11B are plots of incremental pore volume of a RF ultrapurepolymer cryogel and a pyrolyzed RF ultrapure polymer cryogel,respectively.

FIG. 12 depicts the specific surface area vs. activation weight loss forvarious ultrapure synthetic activated carbon materials.

FIG. 13 is a plot of incremental pore volume of an ultrapure syntheticactivated carbon material.

DETAILED DESCRIPTION

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments.However, one skilled in the art will understand that the invention maybe practiced without these details. In other instances, well-knownstructures have not been shown or described in detail to avoidunnecessarily obscuring descriptions of the embodiments. Unless thecontext requires otherwise, throughout the specification and claimswhich follow, the word “comprise” and variations thereof, such as,“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.” Further, headingsprovided herein are for convenience only and do not interpret the scopeor meaning of the claimed invention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment. Thus, the appearances of the phrases “in one embodiment” or“in an embodiment” in various places throughout this specification arenot necessarily all referring to the same embodiment. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments. Also, as used in thisspecification and the appended claims, the singular forms “a,” “an,” and“the” include plural referents unless the content clearly dictatesotherwise. It should also be noted that the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

DEFINITIONS

As used herein, and unless the context dictates otherwise, the followingterms have the meanings as specified below.

“Carbon material” refers to a material or substance comprisedsubstantially of carbon. Carbon materials include both amorphous andcrystalline carbon materials. Examples of carbon materials include, butare not limited to, activated carbon, pyrolyzed dried ultrapure polymergels, pyrolyzed ultrapure polymer cryogels, pyrolyzed ultrapure polymerxerogels, pyrolyzed ultrapure polymer aerogels, activated driedultrapure polymer gels, activated ultrapure polymer cryogels, activatedultrapure polymer xerogels, activated ultrapure polymer aerogels and thelike.

“Amorphous” refers to a material, for example an amorphous carbonmaterial, whose constituent atoms, molecules, or ions are arrangedrandomly without a regular repeating pattern. Amorphous materials mayhave some localized crystallinity (i.e., regularity) but lack long-rangeorder of the positions of the atoms. Pyrolyzed and/or activated carbonmaterials are generally amorphous.

“Crystalline” refers to a material whose constituent atoms, molecules,or ions are arranged in an orderly repeating pattern. Examples ofcrystalline carbon materials include, but are not limited to, diamondand graphene.

“Synthetic” refers to a substance which has been prepared by chemicalmeans rather than from a natural source. For example, a synthetic carbonmaterial is one which is synthesized from precursor materials and is notisolated from natural sources.

“Impurity” or “impurity element” refers to a foreign substance (e.g., anelement) within a material which differs from the chemical compositionof the base material. For example, an impurity in an ultrapure syntheticcarbon material or an ultrapure synthetic amorphous carbon materialrefers to any element or combination of elements, other than carbon,which is present in the ultrapure synthetic carbon material or theultrapure synthetic amorphous carbon material. Impurity levels aretypically expressed in parts per million (ppm).

“PIXE impurity” is any impurity element having an atomic number rangingfrom 11 to 92 (i.e., from sodium to uranium). The phrases “total PIXEimpurity content” and “total PIXE impurity level” both refer to the sumof all PIXE impurities present in a sample, for example, an ultrapurepolymer gel, an ultrapure synthetic carbon material or an ultrapuresynthetic amorphous carbon material. PIXE impurity concentrations andidentities may be determined by proton induced x-ray emission (PIXE).

“Ultrapure” refers to a substance having a total PIXE impurity contentof less than 0.050%. For example, an “ultrapure carbon material”,“ultrapure synthetic carbon material” or “ultrapure synthetic amorphouscarbon material” is a carbon material having a total PIXE impuritycontent of less than 0.050% (i.e., 500 ppm).

“Ash content” refers to the nonvolatile inorganic matter which remainsafter subjecting a substance to a high decomposition temperature.Herein, the ash content of a carbon material is calculated from thetotal PIXE impurity content as measured by proton induced x-rayemission, assuming that nonvolatile elements are completely converted toexpected combustion products (i.e., oxides).

“Polymer” refers to a macromolecule comprised of two or more structuralrepeating units.

“Synthetic polymer precursor material” or “polymer precursor” refers tothe compounds used in the preparation of a synthetic polymer. Examplesof polymer precursors that can be used in the preparations disclosedherein include, but are not limited to aldehydes (i.e., HC(═O)R, where Ris an organic group), such as for example, methanal (formaldehyde);ethanal (acetaldehyde); propanal (propionaldehyde); butanal(butyraldehyde); glucose; benzaldehyde and cinnamaldehyde. Otherexemplary polymer precursors include, but are not limited to, phenoliccompounds such as phenol and polyhydroxy benzenes, such as dihydroxy ortrihydroxy benzenes, for example, resorcinol (i.e., 1,3-dihydroxybenzene), catechol, hydroquinone, and phloroglucinol. Mixtures of two ormore polyhydroxy benzenes are also contemplated within the meaning ofpolymer precursor.

“Monolithic” refers to a solid, three-dimensional structure that is notparticulate in nature.

“Sol” refers to a colloidal suspension of precursor particles (e.g.,polymer precursors), and the term “gel” refers to a wetthree-dimensional porous network obtained by condensation or reaction ofthe precursor particles.

“Polymer gel” refers to a gel in which the network component is apolymer; generally a polymer gel is a wet (aqueous or non-aqueous based)three-dimensional structure comprised of a polymer formed from syntheticprecursors or polymer precursors.

“Sol gel” refers to a sub-class of polymer gel where the polymer is acolloidal suspension that forms a wet three-dimensional porous networkobtained by reaction of the polymer precursors.

“Polymer hydrogel” or “hydrogel” refers to a subclass of polymer gel orgel wherein the solvent for the synthetic precursors or monomers iswater or mixtures of water and one or more water-miscible solvent.

“RF polymer hydrogel” refers to a sub-class of polymer gel wherein thepolymer was formed from the catalyzed reaction of resorcinol andformaldehyde in water or mixtures of water and one or morewater-miscible solvent.

“Acid” refers to any substance that is capable of lowering the pH of asolution. Acids include Arrhenius, Brønsted and Lewis acids. A “solidacid” refers to a dried or granular compound that yields an acidicsolution when dissolved in a solvent. The term “acidic” means having theproperties of an acid.

“Base” refers to any substance that is capable of raising the pH of asolution. Bases include Arrhenius, Brønsted and Lewis bases. A “solidbase” refers to a dried or granular compound that yields basic solutionwhen dissolved in a solvent. The term “basic” means having theproperties of a base.

“Mixed solvent system” refers to a solvent system comprised of two ormore solvents, for example, two or more miscible solvents. Examples ofbinary solvent systems (i.e., containing two solvents) include, but arenot limited to: water and acetic acid; water and formic acid; water andpropionic acid; water and butyric acid and the like. Examples of ternarysolvent systems (i.e., containing three solvents) include, but are notlimited to: water, acetic acid, and ethanol; water, acetic acid andacetone; water, acetic acid, and formic acid; water, acetic acid, andpropionic acid; and the like. The present invention contemplates allmixed solvent systems comprising two or more solvents.

“Miscible” refers to the property of a mixture wherein the mixture formsa single phase over certain ranges of temperature, pressure, andcomposition.

“Catalyst” is a substance which alters the rate of a chemical reaction.Catalysts participate in a reaction in a cyclic fashion such that thecatalyst is cyclically regenerated. The present disclosure contemplatescatalysts which are sodium free. The catalyst used in the preparation ofa ultrapure polymer gel as described herein can be any compound thatfacilitates the polymerization of the polymer precusers to form anultrapure polymer gel. A “volatile catalyst” is a catalyst which has atendency to vaporize at or below atmospheric pressure. Exemplaryvolatile catalysts include, but are not limited to, ammoniums salts,such as ammonium bicarbonate, ammonium carbonate, ammonium hydroxide,and combinations thereof.

“Solvent” refers to a substance which dissolves or suspends reactants(e.g., ultrapure polymer precursors) and provides a medium in which areaction may occur. Examples of solvents useful in the preparation ofthe gels, ultrapure polymer gels, ultrapure synthetic carbon materialsand ultrapure synthetic amorphous carbon materials disclosed hereininclude, but are not limited to, water, alcohols and mixtures thereof.Exemplary alcohols include ethanol, t-butanol, methanol and mixturesthereof. Such solvents are useful for dissolution of the syntheticultrapure polymer precursor materials, for example dissolution of aphenolic or aldehyde compound. In addition, in some processes suchsolvents are employed for solvent exchange in a polymer hydrogel (priorto freezing and drying), wherein the solvent from the polymerization ofthe precursors, for example, resorcinol and formaldehyde, is exchangedfor a pure alcohol. In one embodiment of the present application, acryogel is prepared by a process that does not include solvent exchange.

“Dried gel” or “dried ultrapure polymer gel” refers to a gel orultrapure polymer gel, respectively, from which the solvent, generallywater, or mixture of water and one or more water-miscible solvents, hasbeen substantially removed.

“Pyrolyzed dried ultrapure polymer gel” refers to a dried ultrapurepolymer gel which has been pyrolyzed but not yet activated, while an“activated dried ultrapure polymer gel” refers to a dried ultrapurepolymer gel which has been activated.

“Cryogel” refers to a dried gel that has been dried by freeze drying.Analogously, an “ultrapure polymer cryogel” is a dried ultrapure polymergel that has been dried by freeze drying.

“RF cryogel” or “RF ultrapure polymer cryogel” refers to a dried gel ordried ultrapure polymer gel, respectively, that has been dried by freezedrying wherein the gel or ultrapure polymer gel was formed from thecatalyzed reaction of resorcinol and formaldehyde.

“Pyrolyzed cryogel” or “pyrolyzed ultrapure polymer cryogel” is acryogel or ultrapure polymer cryogel, respectively, that has beenpyrolyzed but not yet activated.

“Activated cryogel” or “activated ultrapure polymer cryogel” is acryogel or ultrapure polymer cryogel, respectively, which has beenactivated to obtain activated carbon material.

“Xerogel” refers to a dried gel that has been dried by air drying, forexample, at or below atmospheric pressure. Analogously, a “ultrapurepolymer xerogel” is a dried ultrapure polymer gel that has been dried byair drying.

“Pyrolyzed xerogel” or “pyrolyzed ultrapure polymer xerogel” is axerogel or ultrapure polymer xerogel, respectively, that has beenpyrolyzed but not yet activated.

“Activated xerogel” or “activated ultrapure polymer xerogel” is axerogel or ultrapure polymer xerogel, respectively, which has beenactivated to obtain activated carbon material.

“Aerogel” refers to a dried gel that has been dried by supercrticaldrying, for example, using supercritical carbon dioxide. Analogously, an“ultrapure polymer aerogel” is a dried ultrapure polymer gel that hasbeen dried by supercritical drying.

“Pyrolyzed aerogel” or “pyrolyzed ultrapure polymer aerogel” is anaerogel or ultrapure polymer aerogel, respectively, that has beenpyrolyzed but not yet activated.

“Activated aerogel” or “activated ultrapure polymer aerogel” is anaerogel or ultrapure polymer aerogel, respectively, which has beenactivated to obtain activated carbon material.

“Organic extraction solvent” refers to an organic solvent added to apolymer hydrogel after polymerization of the polymer precursors hasbegun, generally after polymerization of the polymer hydrogel iscomplete.

“Rapid multi-directional freezing” refers to the process of freezing apolymer gel by creating polymer gel particles from a monolithic polymergel, and subjecting said polymer gel particles to a suitably coldmedium. The cold medium can be, for example, liquid nitrogen, nitrogengas, or solid carbon dioxide. During rapid multi-directional freezingnucleation of ice dominates over ice crystal growth. The suitably coldmedium can be, for example, a gas, liquid, or solid with a temperaturebelow about −10° C. Alternatively, the suitably cold medium can be agas, liquid, or solid with a temperature below about −20° C.Alternatively, the suitably cold medium can be a gas, liquid, or solidwith a temperature below about −30° C.

“Activate” and “activation” each refer to the process of heating a rawmaterial or carbonized/pyrolyzed substance at an activation dwelltemperature during exposure to oxidizing atmospheres (e.g. carbondioxide, oxygen, or steam) to produce an “activated” substance (e.g.activated cryogel or activated carbon material). The activation processgenerally results in a stripping away of the surface of the particles,resulting in an increased surface area. Alternatively, activation can beaccomplished by chemical means, for example, by impregnation ofcarbon-containing precursor materials with chemicals such as acids likephosphoric acid or bases like potassium hydroxide, sodium hydroxide orsalts like zinc chloride, followed by carbonization. “Activated” refersto a material or substance, for example an ultrapure synthetic carbonmaterial or an ultrapure synthetic amorphous carbon material, which hasundergone the process of activation.

“Carbonizing”, “pyrolyzing”, “carbonization” and “pyrolysis” each referto the process of heating a carbon-containing substance at a pyolysisdwell temperature in an inert atmosphere (e.g., argon or nitrogen) or ina vacuum such that the targeted material collected at the end of theprocess is primarily carbon. “Pyrolyzed” refers to a material orsubstance, for example an ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material, which has undergone theprocess of pyrolysis.

“Dwell temperature” refers to the temperature of the furnace during theportion of a process which is reserved for maintaining a relativelyconstant temperature (i.e., neither increasing nor decreasing thetemperature). For example, the pyrolysis dwell temperature refers to therelatively constant temperature of the furnace during pyrolysis, and theactivation dwell temperature refers to the relatively constanttemperature of the furnace during activation.

“Pore” refers to an opening or depression in the surface, or a tunnel ina carbon material, such as for example activated carbon, pyrolyzed driedultrapure polymer gels, pyrolyzed ultrapure polymer cryogels, pyrolyzedultrapure polymer xerogels, pyrolyzed ultrapure polymer aerogels,activated dried ultrapure polymer gels, activated ultrapure polymercryogels, activated ultrapure polymer xerogels, activated ultrapurepolymer aerogels and the like. A pore can be a single tunnel orconnected to other tunnels in a continuous network throughout thestructure.

“Pore structure” refers to the layout of the surface of the internalpores within a carbon material, such as an activated carbon material.Components of the pore structure include pore size, pore volume, surfacearea, density, pore size distribution, and pore length. Generally thepore structure of activated carbon material comprises micropores andmesopores.

“Mesopore” generally refers to pores having a diameter between about 2nanometers and about 50 nanometers while the term “micropore” refers topores having a diameter less than about 2 nanometers.

“Surface area” refers to the total specific surface area of a substancemeasurable by the BET technique. Surface area is typically expressed inunits of m²/g. The BET (Brunauer/Emmett/Teller) technique employs aninert gas, for example nitrogen, to measure the amount of gas adsorbedon a material and is commonly used in the art to determine theaccessible surface area of materials.

“Connected” when used in reference to mesopores and micropores refers tothe spatial orientation of such pores.

“Effective length” refers to the portion of the length of the pore thatis of sufficient diameter such that it is available to accept salt ionsfrom the electrolyte.

“Tunable” refers to an ability to adjust up or down the pore size, porevolume, surface area, density, pore size distribution, pore length orcombinations thereof of either or both of the mesopores and microporesof a carbon material. For example, tunability may refer to adjustingpore size to accommodate targeted electrolyte ions, as appropriate whenthe ultrapure synthetic amorphous carbon materials described herein areemployed as electrode materials. In some embodiments, the pore structureof an ultrapure synthetic carbon material or an ultrapure syntheticamorphous carbon material can be tuned. For example, in the preparationof an ultrapure synthetic carbon material or ultrapure syntheticamorphous carbon material, tuning the pore structure can be accomplisheda number of ways, including but not limited to, varying parameters inthe production of a ultrapure polymer gel; varying parameters in thefreeze-drying of the ultrapure polymer gel; varying parameters in thecarbonizing of the ultrapure polymer cryogel; and varying the parametersin the activation of the pyrolyzed ultrapure polymer cryogel.

“Electrode” refers to a conductor through which electricity enters orleaves an object, substance, or region.

“Binder” refers to a material capable of holding individual particles ofcarbon together such that after mixing a binder and carbon together theresulting mixture can be formed into sheets, pellets, disks or othershapes. Non-exclusive examples of binders include fluoroultrapurepolymers, such as, for example, PTFE (polytetrafluoroethylene, Teflon),PFA (perfluoroalkoxy ultrapure polymer resin, also known as Teflon), FEP(fluorinated ethylene propylene, also known as Teflon), ETFE(polyethylenetetrafluoroethylene, sold as Tefzel and Fluon), PVF(polyvinyl fluoride, sold as Tedlar), ECTFE(polyethylenechlorotrifluoroethylene, sold as Halar), PVDF(polyvinylidene fluoride, sold as Kynar), PCTFE(polychlorotrifluoroethylene, sold as Kel-F and CTFE), trifluoroethanoland combinations thereof.

“Inert” refers to a material that is not active in the electrolyte, thatis it does not absorb a significant amount of ions or change chemically,e.g., degrade.

“Conductive” refers to the ability of a material to conduct electronsthrough transmission of loosely held valence electrons.

“Electrolyte” means a substance containing free ions such that thesubstance is electrically conductive. Examples of electrolytes include,but are not limited to, solvents such as propylene carbonate, ethylenecarbonate, butylene carbonate, dimethyl carbonate, methyl ethylcarbonate, diethyl carbonate, sulfolane, methylsulfolane, acetonitrileor mixtures thereof in combination with solutes such astetralkylammonium salts such as TEA TFB (tetraethylammoniumtetrafluoroborate), MTEATFB (methyltriethylammonium tetrafluoroborate),EMITFB (1 ethyl-3-methylimidazolium tetrafluoroborate),tetraethylammonium, triethylammonium based salts or mixtures thereof. Insome embodiments, the electrolyte can be a water-based acid orwater-based base electrolyte such as mild aqueous sulfuric acid oraqueous potassium hydroxide.

A. Ultrapure Polymer Gels and Ultrapure Synthetic Carbon Material

In one embodiment, an ultrapure synthetic carbon material is provided.In another embodiment, an ultrapure synthetic amorphous carbon materialis provided. As discussed above, electrodes comprising carbon materialshaving residual levels of various impurities (e.g., chlorine, sulfur,metals, etc.) are known to decrease the breakdown voltage of theelectrolyte in which the electrodes are immersed. Thus, these electrodesmust be operated at lower voltages and have a shorter life span thandevices comprising higher purity carbon. The impurities in carbonelectrodes are also thought to contribute to degradation of othercomponents within an EDLC or battery. For example the porous membranewhich separates the two carbon electrodes in an EDLC may be degraded bychlorine or other impurities within the carbon electrode. The ultrapuresynthetic carbon materials and ultrapure synthetic amorphous carbonmaterials disclosed herein are significantly more pure than any knowncarbon materials and are thus expected to improve the operation of anynumber of electrical storage and/or distribution devices.

This high purity of the disclosed carbon materials can be attributed tothe disclosed sol gel process. Applicants have discovered that when oneor more polymer precursors, for example a phenolic compound and analdehyde, are co-polymerized under acidic conditions in the presence ofa volatile basic catalyst, an ultrapure polymer gel results. This is incontrast to other reported methods for the preparation of polymer gelswhich result in polymer gels comprising residual levels of metals and/orother impurities as well as residual levels of reaction solvent and/orextraction solvent. Preparation of Carbon Materials from these ImpurePolymer Gels, for Example by pyrolysis and/or activation, results incarbon materials which are also impure.

Contrary to known methods for the preparation of carbon materials, thedisclosed ultrapure polymer gels allow for the preparation of ultrapuresynthetic carbon materials and ultrapure synthetic amorphous carbonmaterials. For example, the ultrapure polymer gels can be pyrolyzed byheating in an inert atmosphere (e.g., nitrogen) to yield the disclosedcarbon materials comprising a high surface area and high pore volume.These carbon materials can be further activated without the use ofchemical activation techniques—which introduce impurities—to obtain thedisclosed ultrapure activated carbon materials. Such materials findutility in any number of electrical storage and distributionapplications.

The carbon materials prepared by the disclosed method are not onlyultrapure, they also comprise desirable physical properties such as highporosity and high surface area. As with ultrapurity, the high porosityand high surface area of the disclosed carbon materials is a result ofthe unique process disclosed herein. The disclosed process allows forvariation of a number of process parameters to control the physicalproperties of the carbon materials. The combination of ultrapurity, highporosity and high surface area allows for the preparation of electricalstorage and distribution devices having properties superior to knowndevices.

The properties of the disclosed ultrapure polymer gels, ultrapuresynthetic carbon materials and ultrapure synthetic amorphous carbonmaterials, as well as methods for their preparation are discussed inmore detail below.

1. Ultrapure Polymer Gels

Ultrapure polymer gels are intermediates in the preparation of thedisclosed ultrapure carbon materials. As such, the physical and chemicalproperties of the ultrapure polymer gels contribute to the properties ofthe ultrapure carbon materials. Accordingly, in some embodiments theultrapure polymer gel is a dried ultrapure polymer gel, for example, insome embodiments the dried ultrapure polymer gel is an ultrapure polymercryogel. In other embodiments, the dried ultrapure polymer gel is anultrapure polymer xerogel or an ultrapure polymer aerogel. In someembodiments, the ultrapure polymer gels are prepared from phenoliccompounds and aldehyde compounds, for example, in one embodiment, theultrapure polymer gels can be produced from resorcinol and formaldehyde.In other embodiments, the ultrapure polymer gels are produced underacidic conditions. In some embodiments, acidity can be provided bydissolution of a solid acid compound, by employing an acid as thereaction solvent or by employing a mixed solvent system where one of thesolvents is an acid. Preparation of the ultrapure polymer gels isdescribed in more detail below.

The disclosed process comprises polymerization to form a polymer gel inthe presence of a basic volatile catalyst. Accordingly, in someembodiments, the ultrapure polymer gel comprises one or more salts, forexample, in some embodiments the one or more salts are basic volatilesalts. Examples of basic volatile salts include, but are not limited to,ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammoniumhydroxide, and combinations thereof. Accordingly, in some embodiments,the present disclosure provides an ultrapure polymer gel comprisingammonium carbonate, ammonium bicarbonate, ammonium acetate, ammoniumhydroxide, or combinations thereof. In further embodiments, theultrapure polymer gel comprises ammonium carbonate. In other furtherembodiments, the ultrapure polymer gel comprises ammonium acetate.

In one embodiment of any of the aspects or variations described hereinthe ultrapure polymer gel is essentially free of t-butanol. For example,in one embodiment, the ultrapure polymer gel contains less than 1000 ppmt-butanol, less than 100 ppm t-butanol, less than 10 ppm t-butanol, orless than 1 ppm t-butanol.

In another embodiment of any of the aspects or variations describedherein the ultrapure polymer gel is essentially free of acetone. Forexample, in one embodiment, the ultrapure polymer gel contains less than1000 ppm acetone, less than 100 ppm acetone, less than 10 ppm acetone,or less than 1 ppm acetone.

The ultrapure polymer gels comprise low levels of impurities. Thus, insome embodiments, the ultrapure polymer gel comprises carbon, hydrogenand oxygen and a total PIXE impurity content of 1000 ppm or less. Inother embodiments, the total PIXE impurity content of the ultrapurepolymer gel is less than 1000 ppm, less than 800 ppm, less than 500 ppm,less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm or less than 1ppm.

The ultrapure polymer gels may also comprise low ash content which maycontribute to the low ash content of an ultrapure carbon materialprepared therefrom. Thus, in some embodiments, the ash content of theultrapure polymer gel ranges from 0.1% to 0.001%. In other embodiments,the ash content of the ultrapure polymer gel is less than 0.1%, lessthan 0.08%, less than 0.05%, less than 0.03%, less than 0.025%, lessthan 0.01%, less than 0.0075%, less than 0.005% or less than 0.001%.

In other embodiments, the ultrapure polymer gel has a total PIXEimpurity content of less than 500 ppm and an ash content of less than0.08%. In a further embodiment, the ultrapure polymer gel has a totalPIXE impurity content of less than 300 ppm and an ash content of lessthan 0.05%. In another further embodiment, the ultrapure polymer gel hasa total PIXE impurity content of less than 200 ppm and an ash content ofless than 0.02%. In another further embodiment, the ultrapure polymergel has a total PIXE impurity content of less than 200 ppm and an ashcontent of less than 0.01%.

As noted above, polymer gels comprising impurities generally yieldcarbon materials which also comprise impurities. Accordingly, one aspectof the present disclosure is an ultrapure polymer gel with low residualimpurities. The amount of individual PIXE impurities present in theultrapure polymer gel can be determined by proton induced x-rayemission. In some embodiments, the level of sodium present in theultrapure polymer gel is less than 1000 ppm, less than 500 ppm, lessthan 100 ppm, less than 50 ppm, less than 10 ppm, or less than 1 ppm. Insome embodiments, the level of magnesium present in the ultrapurepolymer gel is less than 1000 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. In some embodiments, the level ofaluminum present in the ultrapure polymer gel is less than 1000 ppm,less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than 1ppm. In some embodiments, the level of silicon present in the ultrapurepolymer gel is less than 500 ppm, less than 300 ppm, less than 100 ppm,less than 50 ppm, less than 20 ppm, less than 10 ppm or less than 1 ppm.In some embodiments, the level of phosphorous present in the ultrapurepolymer gel is less than 1000 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. In some embodiments, the level ofsulfur present in the ultrapure polymer gel is less than 1000 ppm, lessthan 100 ppm, less than 50 ppm, less than 30 ppm, less than 10 ppm, lessthan 5 ppm or less than 1 ppm. In some embodiments, the level ofchlorine present in the ultrapure polymer gel is less than 1000 ppm,less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than 1ppm. In some embodiments, the level of potassium present in theultrapure polymer gel is less than 1000 ppm, less than 100 ppm, lessthan 50 ppm, less than 10 ppm, or less than 1 ppm. In other embodiments,the level of calcium present in the ultrapure polymer gel is less than100 ppm, less than 50 ppm, less than 20 ppm, less than 10 ppm, less than5 ppm or less than 1 ppm. In some embodiments, the level of chromiumpresent in the ultrapure polymer gel is less than 1000 ppm, less than100 ppm, less than 50 ppm, less than 10 ppm, less than 5 ppm, less than4 ppm, less than 3 ppm, less than 2 ppm or less than 1 ppm. In otherembodiments, the level of iron present in the ultrapure polymer gel isless than 50 ppm, less than 20 ppm, less than 10 ppm, less than 5 ppm,less than 4 ppm, less than 3 ppm, less than 2 ppm or less than 1 ppm. Inother embodiments, the level of nickel present in the ultrapure polymergel is less than 20 ppm, less than 10 ppm, less than 5 ppm, less than 4ppm, less than 3 ppm, less than 2 ppm or less than 1 ppm. In some otherembodiments, the level of copper present in the ultrapure polymer gel isless than 140 ppm, less than 100 ppm, less than 40 ppm, less than 20ppm, less than 10 ppm, less than 5 ppm, less than 4 ppm, less than 3ppm, less than 2 ppm or less than 1 ppm. In yet other embodiments, thelevel of zinc present in the ultrapure polymer gel is less than 20 ppm,less than 10 ppm, less than 5 ppm, less than 2 ppm or less than 1 ppm.In yet other embodiments, the sum of all PIXE impurities, excludingsodium, magnesium, aluminum, silicon, phosphorous, sulphur, chlorine,potassium, calcium, chromium, iron, nickel, copper and zinc, present inthe ultrapure polymer gel is less than 1000 ppm, less than 500 pm, lessthan 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm,less than 25 ppm, less than 10 ppm or less than 1 ppm. As noted above,in some embodiments other impurities such as hydrogen, oxygen and/ornitrogen may be present in levels ranging from less than 10% to lessthan 0.01%.

In some embodiments, the ultrapure polymer gels comprise PIXE impuritiesnear or below the detection limit of the proton induced x-ray emissionanalysis. For example, in some embodiments, the ultrapure polymer gelscomprise less than 50 ppm sodium, less than 15 ppm magnesium, less than10 ppm aluminum, less than 8 ppm silicon, less than 4 ppm phosphorous,less than 3 ppm sulfur, less than 3 ppm chlorine, less than 2 ppmpotassium, less than 3 ppm calcium, less than 2 ppm scandium, less than1 ppm titanium, less than 1 ppm vanadium, less than 0.5 ppm chromium,less than 0.5 ppm manganese, less than 0.5 ppm iron, less than 0.25 ppmcobalt, less than 0.25 ppm nickel, less than 0.25 ppm copper, less than0.5 ppm zinc, less than 0.5 ppm gallium, less than 0.5 ppm germanium,less than 0.5 ppm arsenic, less than 0.5 ppm selenium, less than 1 ppmbromine, less than 1 ppm rubidium, less than 1.5 ppm strontium, lessthan 2 ppm yttrium, less than 3 ppm zirconium, less than 2 ppm niobium,less than 4 ppm molybdenum, less than 4 ppm, technetium, less than 7 ppmrubidium, less than 6 ppm rhodium, less than 6 ppm palladium, less than9 ppm silver, less than 6 ppm cadmium, less than 6 ppm indium, less than5 ppm tin, less than 6 ppm antimony, less than 6 ppm tellurium, lessthan 5 ppm iodine, less than 4 ppm cesium, less than 4 ppm barium, lessthan 3 ppm lanthanum, less than 3 ppm cerium, less than 2 ppmpraseodymium, less than 2 ppm, neodymium, less than 1.5 ppm promethium,less than 1 ppm samarium, less than 1 ppm europium, less than 1 ppmgadolinium, less than 1 ppm terbium, less than 1 ppm dysprosium, lessthan 1 ppm holmium, less than 1 ppm erbium, less than 1 ppm thulium,less than 1 ppm ytterbium, less than 1 ppm lutetium, less than 1 ppmhafnium, less than 1 ppm tantalum, less than 1 ppm tungsten, less than1.5 ppm rhenium, less than 1 ppm osmium, less than 1 ppm iridium, lessthan 1 ppm platinum, less than 1 ppm silver, less than 1 ppm mercury,less than 1 ppm thallium, less than 1 ppm lead, less than 1.5 ppmbismuth, less than 2 ppm thorium, or less than 4 ppm uranium.

In some specific embodiments, the ultrapure polymer gel comprises lessthan 100 ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur,less than 100 ppm calcium, less than 20 ppm iron, less than 10 ppmnickel, less than 40 ppm copper, less than 5 ppm chromium and less than5 ppm zinc. In other specific embodiments, the ultrapure polymer gelcomprises less than 50 ppm sodium, less than 100 ppm silicon, less than30 ppm sulfur, less than 50 ppm calcium, less than 10 ppm iron, lessthan 5 ppm nickel, less than 20 ppm copper, less than 2 ppm chromium andless than 2 ppm zinc.

In other specific embodiments, the ultrapure polymer gel comprises lessthan 50 ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur,less than 10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel,less than 1 ppm copper, less than 1 ppm chromium and less than 1 ppmzinc.

In some other specific embodiments, the ultrapure polymer gel comprisesless than 100 ppm sodium, less than 50 ppm magnesium, less than 50 ppmaluminum, less than 10 ppm sulfur, less than 10 ppm chlorine, less than10 ppm potassium, less than 1 ppm chromium and less than 1 ppmmanganese.

The disclosed method yields an ultrapure polymer gel comprising a highspecific surface area. Without being bound by theory, it is believedthat the surface area of the ultrapure polymer gel contributes, at leastin part, to the desirable surface area properties of the ultrapuresynthetic amorphous carbon materials. The surface area can be measuredusing the BET technique well-known to those of skill in the art. In oneembodiment of any of the aspects disclosed herein the ultrapure polymergel has a BET specific surface area of at least 150 m²/g, at least 250m²/g, at least 400 m²/g, at least 500 m²/g, at least 600 m²/g or atleast 700 m²/g.

In one embodiment, the ultrapure polymer gel has a BET specific surfacearea of 100 m²/g to 1000 m²/g. Alternatively, the ultrapure polymer gelhas a BET specific surface area of between 150 m²/g and 700 m²/g.Alternatively, the ultrapure polymer gel has a BET specific surface areaof between 400 m²/g and 700 m²/g.

In one embodiment, the ultrapure polymer gel has a tap density of from0.10 g/cc to 0.60 g/cc. In one embodiment, the ultrapure polymer gel hasa tap density of from 0.15 g/cc to 0.25 g/cc. In one embodiment of thepresent disclosure, the ultrapure polymer gel has a BET specific surfacearea of at least 150 m²/g and a tap density of less than 0.60 g/cc.Alternately, the ultrapure polymer gel has a BET specific surface areaof at least 250 m²/g and a tap density of less than 0.4 g/cc. In anotherembodiment, the ultrapure polymer gel has a BET specific surface area ofat least 500 m²/g and a tap density of less than 0.30 g/cc.

In another embodiment of any of the aspects or variations disclosedherein the ultrapure polymer gel comprises a residual water content ofless than 15%, less than 13%, less than 10%, less than 5% or less than1%.

In one embodiment, the ultrapure polymer gel has a fractional porevolume of pores at or below 100 nm that comprises at least 50% of thetotal pore volume, at least 75% of the total pore volume, at least 90%of the total pore volume or at least 99% of the total pore volume. Inanother embodiment, the ultrapure polymer gel has a fractional porevolume of pores at or below 20 nm that comprises at least 50% of thetotal pore volume, at least 75% of the total pore volume, at least 90%of the total pore volume or at least 99% of the total pore volume.

In one embodiment, the ultrapure polymer gel has a fractional poresurface area of pores at or below 100 nm that comprises at least 50% ofthe total pore surface area, at least 75% of the total pore surfacearea, at least 90% of the total pore surface area or at least 99% of thetotal pore surface area. In another embodiment, the ultrapure polymergel has a fractional pore surface area of pores at or below 20 nm thatcomprises at least 50% of the total pore surface area, at least 75% ofthe total pore surface area, at least 90% of the total pore surface orat least 99% of the total pore surface area.

The ultrapure polymer gels can be prepared by the polymerization of oneor more polymer precursors in an appropriate solvent system undercatalytic conditions. Accordingly, in one embodiment the ultrapurepolymer gel is prepared by admixing one or more miscible solvents, oneor more phenolic compounds, one or more aldehydes and one or morecatalysts. For example in a further embodiment the ultrapure polymer gelis prepared by admixing water, acetic acid, resorcinol, formaldehyde andammonium acetate. Preparation of ultrapure polymers gels is discussed inmore detail below.

2. Ultrapure Synthetic Carbon Materials

As noted above, this invention is a directed to a synthetic carbonmaterial which is ultrapure (i.e. less than 500 ppm of total PIXEimpurities). In some embodiments, the synthetic ultrapure carbonmaterial is amorphous. While not wishing to be bound by theory, it isbelieved that the purity and properties of the carbon materials are afunction of its preparation method, and variation of the preparationparameters may yield carbon materials having different properties.Accordingly, in some embodiments, the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material is a pyrolyzeddried ultrapure polymer gel, for example, a pyrolyzed ultrapure polymercryogel, a pyrolyzed ultrapure polymer xerogel or a pyrolyzed ultrapurepolymer aerogel. In other embodiments, the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material is activated(i.e., an ultrapure synthetic activated carbon material). For example,in further embodiments the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material is an activated driedultrapure polymer gel, an activated ultrapure polymer cryogel, anactivated ultrapure polymer xerogel or an activated ultrapure polymeraerogel.

The ultrapure synthetic carbon material and ultrapure syntheticamorphous carbon material comprise low total PIXE impurities. Thus, insome embodiments the total PIXE impurity content in the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial (as measured by proton induced x-ray emission) is less than1000 ppm. In other embodiments, the total PIXE impurity content in theultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material is less than 800 ppm, less than 500 ppm, less than 300ppm, less than 200 ppm, less than 150 ppm, less than 100 ppm, less than50 ppm, less than 25 ppm, less than 10 ppm, less than 5 ppm or less than1 ppm. In further embodiments of the foregoing, the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material is apyrolyzed dried ultrapure polymer gel, a pyrolyzed ultrapure polymercryogel, a pyrolyzed ultrapure polymer xerogel, a pyrolyzed ultrapurepolymer aerogel, an activated dried ultrapure polymer gel, an activatedultrapure polymer cryogel, an activated ultrapure polymer xerogel or anactivated ultrapure polymer aerogel.

In addition to low PIXE impurity content, the disclosed carbon materialscomprise high total carbon content. In addition to carbon, the ultrapuresynthetic carbon material and ultrapure synthetic amorphous carbonmaterial may also comprise oxygen, hydrogen and nitrogen. In someembodiments, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises at least 85% carbon, atleast 90% carbon, at least 95% carbon, at least 96% carbon, at least 97%carbon, at least 98% carbon or at least 99% carbon on a weight/weightbasis. In some other embodiments, the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material comprises lessthan 10% oxygen, less than 5% oxygen, less than 3.0% oxygen, less than2.5% oxygen, less than 1% oxygen or less than 0.5% oxygen on aweight/weight basis. In other embodiments, the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon materialcomprises less than 10% hydrogen, less than 5% hydrogen, less than 2.5%hydrogen, less than 1% hydrogen, less than 0.5% hydrogen or less than0.1% hydrogen on a weight/weight basis. In other embodiments, theultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material comprises less than 5% nitrogen, less than 2.5%nitrogen, less than 1% nitrogen, less than 0.5% nitrogen, less than0.25% nitrogen or less than 0.01% nitrogen on a weight/weight basis. Theoxygen, hydrogen and nitrogen content of the disclosed carbon materialscan be determined by combustion analysis. Techniques for determiningelemental composition by combustion analysis are well known in the art.

The total ash content of a carbon material may, in some instances, havean effect on the electrochemical performance of a carbon material.Accordingly, in some embodiments, the ash content of the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial ranges from 0.1% to 0.001%, for example in some specificembodiments the ash content of the ultrapure synthetic carbon materialor ultrapure synthetic amorphous carbon material is less than 0.1%, lessthan 0.08%, less than 0.05%, less than 0.03%, than 0.025%, less than0.01%, less than 0.0075%, less than 0.005% or less than 0.001%.

In other embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 500 ppm and an ash content of less than 0.08%. Infurther embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 300 ppm and an ash content of less than 0.05%. Inother further embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 200 ppm and an ash content of less than 0.05%. Inother further embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 200 ppm and an ash content of less than 0.025%. Inother further embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 100 ppm and an ash content of less than 0.02%. Inother further embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total PIXE impuritycontent of less than 50 ppm and an ash content of less than 0.01%.

The amount of individual PIXE impurities present in the disclosed carbonmaterials can be determined by proton induced x-ray emission. IndividualPIXE impurities may contribute in different ways to the overallelectrochemical performance of the disclosed carbon materials. Thus, insome embodiments, the level of sodium present in the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material is lessthan 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. In some embodiments, the level ofmagnesium present in the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material is less than 1000 ppm,less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than 1ppm. In some embodiments, the level of aluminum present in the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial is less than 1000 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. In some embodiments, the level ofsilicon present in the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material is less than 500 ppm, less than 300ppm, less than 100 ppm, less than 50 ppm, less than 20 ppm, less than 10ppm or less than 1 ppm. In some embodiments, the level of phosphorouspresent in the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material is less than 1000 ppm, less than 100ppm, less than 50 ppm, less than 10 ppm, or less than 1 ppm. In someembodiments, the level of sulfur present in the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material is lessthan 1000 ppm, less than 100 ppm, less than 50 ppm, less than 30 ppm,less than 10 ppm, less than 5 ppm or less than 1 ppm. In someembodiments, the level of chlorine present in the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material is lessthan 1000 ppm, less than 100 ppm, less than 50 ppm, less than 10 ppm, orless than 1 ppm. In some embodiments, the level of potassium present inthe ultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material is less than 1000 ppm, less than 100 ppm, less than 50ppm, less than 10 ppm, or less than 1 ppm. In other embodiments, thelevel of calcium present in the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material is less than 100 ppm, lessthan 50 ppm, less than 20 ppm, less than 10 ppm, less than 5 ppm or lessthan 1 ppm. In some embodiments, the level of chromium present in theultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material is less than 1000 ppm, less than 100 ppm, less than 50ppm, less than 10 ppm, less than 5 ppm, less than 4 ppm, less than 3ppm, less than 2 ppm or less than 1 ppm. In other embodiments, the levelof iron present in the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material is less than 50 ppm, less than 20ppm, less than 10 ppm, less than 5 ppm, less than 4 ppm, less than 3ppm, less than 2 ppm or less than 1 ppm. In other embodiments, the levelof nickel present in the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material is less than 20 ppm, lessthan 10 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, lessthan 2 ppm or less than 1 ppm. In some other embodiments, the level ofcopper present in the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material is less than 140 ppm, less than 100ppm, less than 40 ppm, less than 20 ppm, less than 10 ppm, less than 5ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm or less than 1ppm. In yet other embodiments, the level of zinc present in theultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material is less than 20 ppm, less than 10 ppm, less than 5 ppm,less than 2 ppm or less than 1 ppm. In yet other embodiments, the sum ofall PIXE impurities, excluding sodium, magnesium, aluminum, silicon,phosphorous, sulphur, chlorine, potassium, calcium, chromium, iron,nickel, copper and zinc, present in the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material is less than1000 ppm, less than 500 pm, less than 300 ppm, less than 200 ppm, lessthan 100 ppm, less than 50 ppm, less than 25 ppm, less than 10 ppm orless than 1 ppm. As noted above, in some embodiments other impuritiessuch as hydrogen, oxygen and/or nitrogen may be present in levelsranging from less than 10% to less than 0.01%.

In some embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises PIXE impuritiesnear or below the detection limit of the proton induced x-ray emissionanalysis. For example, in some embodiments the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon materialcomprises less than 50 ppm sodium, less than 15 ppm magnesium, less than10 ppm aluminum, less than 8 ppm silicon, less than 4 ppm phosphorous,less than 3 ppm sulfur, less than 3 ppm chlorine, less than 2 ppmpotassium, less than 3 ppm calcium, less than 2 ppm scandium, less than1 ppm titanium, less than 1 ppm vanadium, less than 0.5 ppm chromium,less than 0.5 ppm manganese, less than 0.5 ppm iron, less than 0.25 ppmcobalt, less than 0.25 ppm nickel, less than 0.25 ppm copper, less than0.5 ppm zinc, less than 0.5 ppm gallium, less than 0.5 ppm germanium,less than 0.5 ppm arsenic, less than 0.5 ppm selenium, less than 1 ppmbromine, less than 1 ppm rubidium, less than 1.5 ppm strontium, lessthan 2 ppm yttrium, less than 3 ppm zirconium, less than 2 ppm niobium,less than 4 ppm molybdenum, less than 4 ppm, technetium, less than 7 ppmrubidium, less than 6 ppm rhodium, less than 6 ppm palladium, less than9 ppm silver, less than 6 ppm cadmium, less than 6 ppm indium, less than5 ppm tin, less than 6 ppm antimony, less than 6 ppm tellurium, lessthan 5 ppm iodine, less than 4 ppm cesium, less than 4 ppm barium, lessthan 3 ppm lanthanum, less than 3 ppm cerium, less than 2 ppmpraseodymium, less than 2 ppm, neodymium, less than 1.5 ppm promethium,less than 1 ppm samarium, less than 1 ppm europium, less than 1 ppmgadolinium, less than 1 ppm terbium, less than 1 ppm dysprosium, lessthan 1 ppm holmium, less than 1 ppm erbium, less than 1 ppm thulium,less than 1 ppm ytterbium, less than 1 ppm lutetium, less than 1 ppmhafnium, less than 1 ppm tantalum, less than 1 ppm tungsten, less than1.5 ppm rhenium, less than 1 ppm osmium, less than 1 ppm iridium, lessthan 1 ppm platinum, less than 1 ppm silver, less than 1 ppm mercury,less than 1 ppm thallium, less than 1 ppm lead, less than 1.5 ppmbismuth, less than 2 ppm thorium, or less than 4 ppm uranium.

In some specific embodiments, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises less than 100ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc as measured by proton induced x-ray emission. In other specificembodiments, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises less than 50 ppm sodium,less than 30 ppm sulfur, less than 100 ppm silicon, less than 50 ppmcalcium, less than 10 ppm iron, less than 5 ppm nickel, less than 20 ppmcopper, less than 2 ppm chromium and less than 2 ppm zinc.

In other specific embodiments, the ultrapure synthetic carbon materialor ultrapure synthetic amorphous carbon material comprises less than 50ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, less than10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, less than1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc.

In some other specific embodiments, the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material comprises lessthan 100 ppm sodium, less than 50 ppm magnesium, less than 50 ppmaluminum, less than 10 ppm sulfur, less than 10 ppm chlorine, less than10 ppm potassium, less than 1 ppm chromium and less than 1 ppmmanganese.

The disclosed carbon materials comprise a high surface area. While notwishing to be bound by theory, it is thought that such high surface areamay contribute to the high energy density obtained from devicescomprising the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material. Accordingly, in some embodiment,the ultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material comprises a BET specific surface area of at least 1000m²/g, at least 1500 m²/g, at least 2000 m²/g, at least 2400 m²/g, atleast 2500 m²/g, at least 2750 m²/g or at least 3000 m²/g. For example,in some embodiments of the foregoing, the ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material is activated.

In another embodiment, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a tap density between0.2 and 0.6 g/cc, between 0.3 and 0.5 g/cc or between 0.4 and 0.5 g/cc.In another embodiment, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material has a total pore volume ofat least 0.5 cm³/g, at least 0.7 cm³/g, at least 0.75 cm³/g, at least0.9 cm³/g, at least 1.0 cm³/g, at least 1.1 cm³/g, at least 1.2 cm³/g,at least 1.3 cm³/g, at least 1.4 cm³/g, at least 1.5 cm³/g or at least1.6 cm³/g.

The pore size distribution of the disclosed carbon materials is oneparameter that may have an effect on the electrochemical performance ofthe synthetic amorphous carbon materials. For example, a carbon materialcomprising pores sized to accommodate specific electrolyte ions may beparticularly useful in EDLC devices. In addition, carbon materialscomprising mesopores with a short effective length (i.e., less than 10nm, less than 5, nm or less than 3 nm as measured by TEM) may be usefulto enhance ion transport and maximize power. Accordingly, in oneembodiment, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises a fractional pore volumeof pores at or below 100 nm that comprises at least 50% of the totalpore volume, at least 75% of the total pore volume, at least 90% of thetotal pore volume or at least 99% of the total pore volume. In otherembodiments, the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material comprises a fractional pore volumeof pores at or below 20 nm that comprises at least 50% of the total porevolume, at least 75% of the total pore volume, at least 90% of the totalpore volume or at least 99% of the total pore volume.

In another embodiment, the ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material comprises a fractionalpore surface area of pores at or below 100 nm that comprises at least50% of the total pore surface area, at least 75% of the total poresurface area, at least 90% of the total pore surface area or at least99% of the total pore surface area. In another embodiment, the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a fractional pore surface area of pores at or below20 nm that comprises at least 50% of the total pore surface area, atleast 75% of the total pore surface area, at least 90% of the total poresurface area or at least 99% of the total pore surface area.

In another embodiment of the present disclosure, the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material isprepared by a method disclosed herein, for example, in some embodimentsthe ultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material is prepared by a method comprising pyrolyzing a driedultrapure polymer gel as disclosed herein. In some embodiments, thepyrolyzed ultrapure polymer gel is further activated to obtain anultrapure synthetic activated carbon material or an ultrapure syntheticamorphous carbon material. Methods for preparation of the disclosedcarbon materials are described in more detail below.

B. Preparation of Ultrapure Synthetic Amorphous Carbon Materials

In one embodiment, a method for preparing novel ultrapure polymer gelsis provided. In another embodiment, a method for preparing ultrapuresynthetic carbon materials is provided, for example, in someembodiments, the ultrapure synthetic carbon material is an ultrapuresynthetic amorphous carbon material. Such ultrapure polymer gels andultrapure synthetic carbon materials cannot be obtained by previouslyreported methods. In some further embodiments, a method for preparingultrapure synthetic activated carbon materials, for example ultrapuresynthetic amorphous activated carbon materials, is provided. Details ofthe variable process parameters of the various embodiments of thedisclosed methods are described below.

1. Preparation of Ultrapure Polymer Gels

The ultrapure polymer gels may be prepared by a sol gel process. Forexample, the ultrapure polymer gel may be prepared by co-polymerizingone or more polymer precursors in an appropriate solvent. In oneembodiment, the one or more polymer precursors are co-polymerized underacidic conditions. In some embodiments, a first polymer precursor is aphenolic compound and a second polymer precursor is an aldehydecompound. In one embodiment, of the method the phenolic compound isresorcinol, catechol, hydroquinone, phloroglucinol, phenol, or acombination thereof; and the aldehyde compound is formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde,cinnamaldehyde, or a combination thereof. In a further embodiment, thephenolic compound is resorcinol, phenol or a combination thereof, andthe aldehyde compound is formaldehyde. In yet further embodiments, thephenolic compound is resorcinol and the aldehyde compound isformaldehyde.

The sol gel polymerization process is generally performed undercatalytic conditions. Accordingly, in some embodiments, preparing theultrapure polymer gel comprises co-polymerizing one or more polymerprecursors in the presence of a catalyst. In some embodiments, thecatalyst comprises a basic volatile catalyst. For example, in oneembodiment, the basic volatile catalyst comprises ammonium carbonate,ammonium bicarbonate, ammonium acetate, ammonium hydroxide, orcombinations thereof. In a further embodiment, the basic volatilecatalyst is ammonium carbonate. In another further embodiment, the basicvolatile catalyst is ammonium acetate.

The molar ratio of catalyst to phenolic compound may have an effect onthe final properties of the ultrapure polymer gel as well as the finalproperties of the ultrapure synthetic carbon materials, for example,ultrapure synthetic amorphous carbon materials, prepared therefrom.Thus, in some embodiments such catalysts are used in the range of molarratios of 10:1 to 2000:1 phenolic compound:catalyst. In someembodiments, such catalysts can be used in the range of molar ratios of20:1 to 200:1 phenolic compound:catalyst. For example in otherembodiments, such catalysts can be used in the range of molar ratios of25:1 to 100:1 phenolic compound:catalyst.

The reaction solvent is another process parameter that may be varied toobtain the desired properties of the ultrapure polymer gels andsynthetic amorphous carbon materials. In some embodiments, the solventfor preparation of the ultrapure polymer gel is a mixed solvent systemof water and a miscible co-solvent. For example, in certain embodimentsthe solvent comprises a water miscible acid. Examples of water miscibleacids include, but are not limited to, propionic acid, acetic acid, andformic acid. In further embodiments, the solvent comprises a ratio ofwater-miscible acid to water of 99:1, 90:10, 75:25, 50:50, 25:75, 10:90or 1:90. In other embodiments, acidity is provided by adding a solidacid to the reaction solvent.

In some other embodiments of the foregoing, the solvent for preparationof the ultrapure polymer gel is acidic. For example, in certainembodiments the solvent comprises acetic acid. For example, in oneembodiment, the solvent is 100% acetic acid. In other embodiments, amixed solvent system is provided, wherein one of the solvents is acidic.For example, in one embodiment of the method the solvent is a binarysolvent comprising acetic acid and water. In further embodiments, thesolvent comprises a ratio of acetic acid to water of 99:1, 90:10, 75:25,50:50, 25:75, 10:90 or 1:90. In other embodiments, acidity is providedby adding a solid acid to the reaction solvent.

Some embodiments of the disclosed method do not comprise a solventexchange step (e.g., exchange t-butanol for water) prior tolyophilization. For example, in one embodiment of any of the methodsdescribed herein, before freezing, the ultrapure polymer gel orultrapure polymer gel particles are rinsed with water. In oneembodiment, the average diameter of said ultrapure polymer gel particlesprior to freezing is less than 25 mm, for example, between 0.001 mm and25 mm; alternately, the average diameter of said ultrapure polymer gelparticles prior to freezing is between 0.01 mm and 15 mm, for example,between 1.0 mm and 15 mm. In some examples, the ultrapure polymer gelparticles are between 1 mm and 10 mm. In further embodiments, theultrapure polymer gel particles are frozen via immersion in a mediumhaving a temperature of below about −10° C., for example, below about−20° C., or alternatively below about −30° C. For example, the mediummay be liquid nitrogen or ethanol (or other organic solvent) in dry iceor ethanol cooled by another means. In some embodiments, drying undervacuum comprises subjecting the frozen particles to a vacuum pressure ofbelow about 1400 mTorr.

Other methods of rapidly freezing the ultrapure polymer gel particlesare also envisioned. In another embodiment, the ultrapure polymer gel israpidly frozen by co-mingling or physical mixing of ultrapure polymergel particles with a suitable cold solid, for example, dry ice (solidcarbon dioxide). Another method is to use a blast freezer with a metalplate at −60° C. to rapidly remove heat from the ultrapure polymer gelparticles scattered over its surface. A third method of rapidly coolingwater in a ultrapure polymer gel particle is to snap freeze the particleby pulling a high vacuum very rapidly (the degree of vacuum is such thatthe temperature corresponding to the equilibrium vapor pressure allowsfor freezing). Yet another method for rapid freezing comprises admixinga ultrapure polymer gel with a suitably cold gas. In some embodimentsthe cold gas may have a temperature below about −10° C. In someembodiments the cold gas may have a temperature below about −20° C. Insome embodiments the cold gas may have a temperature below about −30° C.In yet other embodiments, the gas may have a temperature of about −196°C. For example, in some embodiments, the gas is nitrogen.

In other embodiments, the ultrapure polymer gel particles are frozen ona lyophilizer shelf at a temperature of −20° C. or lower. For example,in some embodiments the ultrapure polymer gel particles are frozen onthe lyophilizer shelf at a temperature of −30° C. or lower. In someother embodiments, the ultrapure polymer gel monolith is subjected to afreeze thaw cycle (from room temperature to −20° C. or lower and back toroom temperature), physical disruption of the freeze-thawed gel tocreate particles, and then further lyophilization processing. Forexample, in some embodiments, the ultrapure polymer gel monolith issubjected to a freeze thaw cycle (from room temperature to −30° C. orlower and back to room temperature), physical disruption of thefreeze-thawed gel to create particles, and then further lyophilizationprocessing.

In some embodiments of the methods described herein, the molar ratio ofphenolic precursor to catalyst is from about 10:1 to about 2000:1 or themolar ratio of phenolic precursor to catalyst is from about 20:1 toabout 200:1. In further embodiments, the molar ratio of phenolicprecursor to catalyst is from about 25:1 to about 100:1. In furtherembodiments, the molar ratio of phenolic precursor to catalyst is fromabout 25:1 to about 50:1. In further embodiments, the molar ratio ofphenolic precursor to catalyst is from about 100:1 to about 50:1.

In the specific embodiment wherein one of the polymer precursors isresorcinol and another polymer precursor is formaldehyde, the resorcinolto catalyst ratio can be varied to obtain the desired properties of theresultant ultrapure polymer gel and synthetic amorphous carbonmaterials. In some embodiments of the methods described herein, themolar ratio of resorcinol to catalyst is from about 10:1 to about 2000:1or the molar ratio of resorcinol to catalyst is from about 20:1 to about200:1. In further embodiments, the molar ratio of resorcinol to catalystis from about 25:1 to about 100:1. In further embodiments, the molarratio of resorcinol to catalyst is from about 25:1 to about 50:1. Infurther embodiments, the molar ratio of resorcinol to catalyst is fromabout 100:1 to about 50:1.

Polymerization to form an ultrapure polymer gel can be accomplished byvarious means described in the art. For instance, polymerization can beaccomplished by incubating suitable polymer precursor materials in thepresence of a suitable catalyst for a period of time. The time forpolymerization can be a period ranging from minutes or hours to days,depending on temperature (the higher the temperature the faster, thereaction rate, and correspondingly, the shorter the time required). Thepolymerization temperature can range from room temperature to atemperature approaching (but lower than) the boiling point of thestarting solution. For example, the temperature can range from about 20°C. to about 90° C. In the specific embodiment wherein one polymerprecursor is resorcinol and one polymer precursor is formaldehyde, thetemperature can range from about 20° C. to about 100° C., typically fromabout 25° C. to about 90° C. In some embodiments, polymerization can beaccomplished by incubation of suitable synthetic polymer precursormaterials in the presence of a catalyst for at least 24 hours at about90° C. Generally polymerization can be accomplished in between about 6and about 24 hours at about 90° C., for example between about 18 andabout 24 hours at about 90° C.

The polymer precursor materials as disclosed herein include (a)alcohols, phenolic compounds, and other mono- or polyhydroxy compoundsand (b) aldehydes, ketones, and combinations thereof. Representativealcohols in this context include straight chain and branched, saturatedand unsaturated alcohols. Suitable phenolic compounds includepolyhydroxy benzene, such as a dihydroxy or trihydroxy benzene.Representative polyhydroxy benzenes include resorcinol (i.e.,1,3-dihydroxy benzene), catechol, hydroquinone, and phloroglucinol.Mixtures of two or more polyhydroxy benzenes can also be used. Phenol(monohydroxy benzene) can also be used. Representative polyhydroxycompounds include sugars, such as glucose, and other polyols, such asmannitol. Aldehydes in this context include: straight chain saturatedaldehydes such as methanal (formaldehyde), ethanal (acetaldehyde),propanal (propionaldehyde), butanal (butyraldehyde), and the like;straight chain unsaturated aldehydes such as ethenone and other ketenes,2-propenal (acrylaldehyde), 2-butenal (crotonaldehyde), 3 butenal, andthe like; branched saturated and unsaturated aldehydes; andaromatic-type aldehydes such as benzaldehyde, salicylaldehyde,hydrocinnamaldehyde, and the like. Suitable ketones include: straightchain saturated ketones such as propanone and 2 butanone, and the like;straight chain unsaturated ketones such as propenone, 2 butenone, and3-butenone(methyl vinyl ketone) and the like; branched saturated andunsaturated ketones; and aromatic-type ketones such as methyl benzylketone (phenylacetone), ethyl benzyl ketone, and the like. The ultrapurepolymer precursor materials can also be combinations of the precursorsdescribed above.

In some embodiments, one polymer precursor is an alcohol-containingspecies and another polymer precursor is a carbonyl-containing species.The relative amounts of alcohol-containing species (e.g. alcohols,phenolic compounds and mono- or poly-hydroxy compounds or combinationsthereof) reacted with the carbonyl containing species (e.g. aldehydes,ketones or combinations thereof) can vary substantially. In someembodiments, the ratio of alcohol-containing species to aldehyde speciesis selected so that the total moles of reactive alcohol groups in thealcohol-containing species is approximately the same as the total molesof reactive carbonyl groups in the aldehyde species. Similarly, theratio of alcohol-containing species to ketone species may be selected sothat the total moles of reactive alcohol groups in the alcoholcontaining species is approximately the same as the total moles ofreactive carbonyl groups in the ketone species. The same general 1:1molar ratio holds true when the carbonyl-containing species comprises acombination of an aldehyde species and a ketone species.

The total solids content in the aqueous solution prior to ultrapurepolymer gel formation can be varied. The weight ratio of resorcinol towater is from about 0.05 to 1 to about 0.70 to 1. Alternatively, theratio of resorcinol to water is from about 0.15 to 1 to about 0.6 to 1.Alternatively, the ratio of resorcinol to water is from about 0.15 to 1to about 0.35 to 1. Alternatively, the ratio of resorcinol to water isfrom about 0.25 to 1 to about 0.5 to 1. Alternatively, the ratio ofresorcinol to water is from about 0.3 to 1 to about 0.4 to 1.

Examples of solvents useful in the preparation of the ultrapure polymergels disclosed herein include but are not limited to water or alcoholsuch as, for example, ethanol, t butanol, methanol or mixtures of these,optionally further with water. Such solvents are useful for dissolutionof the polymer precursor materials, for example dissolution of thephenolic compound. In addition, in some processes such solvents areemployed for solvent exchange in the ultrapure polymer gel (prior tofreezing and drying), wherein the solvent from the ultrapurepolymerization of the precursors, for example, resorcinol andformaldehyde, is exchanged for a pure alcohol. In one embodiment of thepresent application, an ultrapure polymer gel is prepared by a processthat does not include solvent exchange.

Suitable catalysts in the preparation of ultrapure polymer gels includevolatile basic catalysts that facilitate polymerization of the precursormaterials into a monolithic ultrapure polymer. The catalyst can alsocomprise various combinations of the catalysts described above. Inembodiments comprising phenolic compounds, such catalysts can be used inthe range of molar ratios of 20:1 to 200:1 phenolic compound:catalyst.For example, in some specific embodiments such catalysts can be used inthe range of molar ratios of 25:1 to 100:1 phenolic compound:catalyst.

2. Creation of Ultrapure Polymer Gel Particles

A monolithic ultrapure polymer gel can be physically disrupted to createsmaller particles according to various techniques known in the art. Theresultant ultrapure polymer gel particles generally have an averagediameter of less than about 30 mm, for example, in the size range ofabout 1 mm to about 25 mm, or between about 1 mm to about 5 mm orbetween about 0.5 mm to about 10 mm. Alternatively, the size of theultrapure polymer gel particles can be in the range below about 1 mm,for example, in the size range of about 10 to 1000 microns. Techniquesfor creating ultrapure polymer gel particles from monolithic materialinclude manual or machine disruption methods, such as sieving, grinding,milling, or combinations thereof. Such methods are well-known to thoseof skill in the art. Various types of mills can be employed in thiscontext such as roller, bead, and ball mills and rotary crushers andsimilar particle creation equipment known in the art.

In a specific embodiment, a roller mill is employed. A roller mill hasthree stages to gradually reduce the size of the gel particles. Theultrapure polymer gels are generally very brittle for a ‘wet’ materialand are not damp to the touch. Consequently they are easily milled usingthis approach, however, the width of each stage must be setappropriately to achieve the targeted final mesh. This adjustment ismade and validated for each combination of gel recipe and mesh size.Each gel is milled via passage through a sieve of known mesh size.Sieved particles can be temporarily stored in sealed containers.

In one embodiment, a rotary crusher is employed. The rotary crusher hasa screen mesh size of about ⅛^(th) inch. In another embodiment, therotary crusher has a screen mesh size of about ⅜^(th) inch. In anotherembodiment, the rotary crusher has a screen mesh size of about ⅝^(th)inch. In another embodiment, the rotary crusher has a screen mesh sizeof about ⅜^(th) inch.

Milling can be accomplished at room temperature according to methodswell known to those of skill in the art. Alternatively, milling can beaccomplished cryogenically, for example by co-milling the ultrapurepolymer gel with solid carbon dioxide (dry ice) particles. In thisembodiment, the two steps of (a) creating particles from the monolithicultrapure polymer gel and (b) rapid, multidirectional freezing of theultrapure polymer gel are accomplished in a single process.

3. Rapid Freezing of Ultrapure Polymer Gels

After the ultrapure polymer gel particles are formed from the monolithicultrapure polymer gel, freezing of the ultrapure polymer gel particlesis accomplished rapidly and in a multi-directional fashion as describedin more detail above. Freezing slowly and in a unidirectional fashion,for example by shelf freezing in a lyophilizer, results in driedmaterial having a very low surface area as evidenced in an exampleherein. Similarly, snap freezing (i.e., freezing that is accomplished byrapidly cooling the ultrapure polymer gel particles by pulling a deepvacuum) also results in a dried material having a low surface area. Asdisclosed herein rapid freezing in a multidirectional fashion can beaccomplished by rapidly lowering the material temperature to at leastabout −10° C. or lower, for example, −20° C. or lower, or for example,to at least about −30° C. or lower. Rapid freezing of the ultrapurepolymer gel particles creates a fine ice crystal structure within theparticles due to widespread nucleation of ice crystals, but leaveslittle time for ice crystal growth. This provides a high specificsurface area between the ice crystals and the hydrocarbon matrix, whichis necessarily excluded from the ice matrix.

The concept of extremely rapid freezing to promote nucleation overcrystal growth can be applied to mixed solvent systems. In oneembodiment, as the mixed solvent system is rapidly cooled, the solventcomponent that predominates will undergo crystallization at itsequilibrium melting temperature, with increased concentration of theco-solvent(s) and concomitant further freezing point depression. As thetemperature is further lowered, there is increased crystallization ofthe predominant solvent and concentration of co-solvent(s) until theeutectic composition is reached, at which point the eutectic compositionundergoes the transtion from liquid to solid without further componentconcentration nor product cooling until complete freezing is achieved.In the specific case of water and acetic acid (which as pure substancesexhibit freezing points of 0° C. and 17° C., respectively), the eutecticcomposition is comprised of approximately 59% acetic acid and 41% waterand freezes at about −27° C. Accordingly, in one embodiment, the mixedsolvent system is the eutectic composition, for example, in oneembodiment the mixed solvent system comprises 59% acetic acid and 41%water.

4. Drying of Ultrapure Polymer Gels

In one embodiment, the frozen ultrapure polymer gel particles containinga fine ice matrix are lyophilized under conditions designed to avoidcollapse of the material and to maintain fine surface structure andporosity in the dried product. Details of the conditions of thelyophilization are provided herein. Generally drying is accomplishedunder conditions where the temperature of the product is kept below atemperature that would otherwise result in collapse of the productpores, thereby enabling the dried material to retain an extremely highsurface area.

One benefit of having an extremely high surface area in the driedproduct is the improved utility of the ultrapure polymer gel for thepurpose of fabrication of capacitors, energy storage devices, and otherenergy-related applications. Different ultrapure polymer gelapplications require variations in the pore size distribution such asdifferent levels of micropore volume, mesopore volume, surface area, andpore size. By tuning the various processing parameters of the ultrapurepolymer gel, high pore volumes can be reached at many different poresizes depending on the desired application.

The structure of the final carbon material is reflected in the structureof the ultrapure dried polymer gel which in turn is established by theultrapure polymer gel properties. These features can be created in theultrapure polymer gel using a sol-gel processing approach as describedherein, but if care is not taken in removal of the solvent, then thestructure is not preserved. It is of interest to both retain theoriginal structure of the ultrapure polymer gel and modify its structurewith ice crystal formation based on control of the freezing process. Insome embodiments, prior to drying the aqueous content of the ultrapurepolymer gel is in the range of about 50% to about 99%. In certainembodiments, upon drying the aqueous content of the ultrapure polymercryogel is than about 10%, alternately less than about 5% or less thanabout 2.5%.

Differential scanning calorimetry (DSC) data for an ultrapure polymerhydrogel demonstrates a large exothermic event at ˜−18° C. These dataare consistent with freezing of water inside a pore of ˜4 nm radius.These findings indicate that the extremely rapid freezing for thepurposes of the current application not only constitutes a rapidfreezing rate, but also that the extent of the decrease is such that thematerial is brought below at least −18° C.

The DSC data also demonstrate that upon warming, there is a broad,complex endothermic behavior, with the onset about −13° C. and amidpoint of about −10° C. There appears to be a thermal transition atabout −2° C., and final melting at about +1° C. The various events maycorrespond to melting of different types of microstructures. The datasuggest that in order to avoid loss of fine product structure in thefrozen state, product temperature during initial (e.g., primary) dryingshould be maintained below −13° C. This is accomplished, for example, ina drying step where heat transfer during primary drying is dominated byconvection rather than conduction, thus the product temperature duringsublimation will correspond to the temperature of ice at equilibriumwith the chamber pressure.

A lyophilizer chamber pressure of about 2250 microns results in aprimary drying temperature in the drying product of about −10° C. Dryingat about 2250 micron chamber pressure or lower case provides a producttemperature during primary drying that is no greater than about −10° C.As a further illustration, a chamber pressure of about 1500 micronsresults in a primary drying temperature in the drying product of about−15° C. Drying at about 1500 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−15° C. As yet a further illustration, a chamber pressure of about 750microns results in a primary drying temperature in the drying product ofabout −20° C. Drying at 750 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−20° C. As yet a further illustration, a chamber pressure of about 300microns results in a primary drying temperature in the drying product ofabout −30° C. Drying at 300 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−30° C.

5. Pyrolysis and Activation of Ultrapure Polymer Gels

In another embodiment, a method for making an ultrapure syntheticactivated carbon material, for example an ultrapure synthetic activatedamorphous carbon material, is provided comprising pyrolysis andactivation of a dried polymer gel disclosed herein. In some embodimentsof the present disclosure, an ultrapure synthetic activated carbonmaterial or ultrapure synthetic activated amorphous carbon materialhaving a specific surface area of at least 1000 m²/g, at least 1500m²/g, at least 2000 m²/g, at least 2400 m²/g, at least 2500 m²/g or atleast 3000 m²/g is provided.

Generally, in the pyrolysis process, dried ultrapure polymer gels areweighed and placed in a rotary kiln. The temperature ramp is set at 5°C. per minute, the dwell time and dwell temperature are set; cool downis determined by the natural cooling rate of the furnace. The entireprocess is usually run under an inert atmosphere, such as a nitrogenenvironment. Pyrolyzed samples are then removed and weighed. Otherpyrolysis processes are well known to those of skill in the art.

In some embodiments, pyrolysis dwell time (the period of time duringwhich the sample is at the desired temperature) is from about 0 minutesto about 120 minutes, from about 0 minutes to about 60 minutes, fromabout 0 minutes to about 30 minutes, from about 0 minutes to about 10minutes, from about 0 to 5 minutes or from about 0 to 1 minute.

Pyrolysis may also be carried out more slowly than described above. Forexample, in one embodiment the pyrolysis is carried out in about 120 to480 minutes. In other embodiments, the pyrolysis is carried out in about120 to 240 minutes.

In some embodiments, pyrolysis dwell temperature ranges from about 650°C. to 1800° C. In other embodiments pyrolysis dwell temperature rangesfrom about 700° C. to about 1200° C. In other embodiments pyrolysisdwell temperature ranges from about 850° C. to about 1050° C. In otherembodiments pyrolysis dwell temperature ranges from about 800° C. toabout 900° C.

In some embodiments, the pyrolysis dwell temperature is varied duringthe course of pyrolysis. In one embodiment, the pyrolysis is carried outin a rotary kiln with separate distinct heating zones, the temperaturefor each zone is sequentially decreased from the entrance to the exitend of the rotary kiln tube. In one embodiment, the pyrolysis is carriedout in a rotary kiln with separate distinct heating zones, thetemperature for each zone is sequentially increased from entrance toexit end of the rotary kiln tube. In one embodiment, the entrance end ofthe heating zone is set at 690° C., the middle of the heating zone isset at 750° C. and the exit end of the heating zone is set at 850° C.

Activation time and activation temperature both have a large impact onthe performance of the resulting activated carbon material, as well asthe manufacturing cost thereof. Increasing the activation temperatureand the activation dwell time results in higher activation percentages,which generally correspond to the removal of more material compared tolower temperatures and shorter dwell times. Activation temperature canalso alter the pore structure of the carbon where lower temperaturesresult in more microporous carbon and higher temperatures result inmesoporosity. This is a result of the activation gas diffusion limitedreaction that occurs at higher temperatures and reaction kinetic drivenreactions that occur at lower temperature. Higher activation percentageoften increases performance of the final activated carbon, but it alsoincreases cost by reducing overall yield. Improving the level ofactivation corresponds to achieving a higher performance product at alower cost.

Pyrolyzed ultrapure polymer gels may be activated by contacting thepyrolyzed ultrapure polymer gel with an activating agent. Many gases aresuitable for activating, for example gases which contain oxygen.Non-limiting examples of activating gases include carbon dioxide, carbonmonoxide, steam, and oxygen. Activating agents may also includecorrosive chemicals such as acids, bases or salts (e.g., phosphoricacid, potassium hydroxide, sodium hydroxide, zinc chloride, etc.). Otheractivating agents are known to those skilled in the art.

In some embodiments, the activation time is between 1 minute and 48hours. In other embodiments, the activation time is between 1 minute and24 hours. In other embodiments, the activation time is between 5 minutesand 24 hours. In other embodiments, the activation time is between 1hour and 24 hours. In further embodiments, the activation time isbetween 12 hours and 24 hours. In certain other embodiments, theactivation time is between 30 min and 4 hours. In some furtherembodiments, the activation time is between 1 hour and 2 hours.

Generally, in the activation process, samples are weighed and placed ina rotary kiln, for which the automated gas control manifold is set toramp at a 20° C. per minute rate. Carbon dioxide is introduced to thekiln environment for a period of time once the proper activationtemperature has been reached. After activation has occurred, the carbondioxide is replaced by nitrogen and the kiln is cooled down. Samples areweighed at the end of the process to assess the level of activation.Other activation processes are well known to those of skill in the art.In some of the embodiments disclosed herein, activation temperatures mayrange from 800° C. to 1300° C. In another embodiment, activationtemperatures may range from 800° C. to 1050° C. In another embodiment,activation temperatures may range from about 850° C. to about 950° C.One skilled in the art will recognize that other activationtemperatures, either lower or higher, may be employed.

The degree of activation is measured in terms of the mass percent of thepyrolyzed dried ultrapure polymer gel that is lost during the activationstep. In one embodiment of the methods described herein, activatingcomprises a degree of activation from 5% to 90%; or a degree ofactivation from 10% to 80%; in some cases activating comprises a degreeof activation from 40% to 70%, or a degree of activation from 45% to65%.

In the methods disclosed herein for the production of high surface areaultrapure synthetic activated carbon materials, the ultrapure polymergel is engineered to produce a material which is already highly porousand contains within its ultrapure polymer framework a carbonic structurewhich, when pyrolyzed and activated, will produce an activated carbonmaterial that contains a targeted mix of mesopores and micropores. Byproducing ultrapure polymer gel with the appropriate targeted mix ofmeso- and micro-pores, the amount of required activation is reduced,thereby improving yield and reducing cost. Also, the ability to tune theproperties (e.g. pore size) of the intermediates introduces a degree oftunability that has not been realized by a more traditional approach ofpyrolyzing and over-activating existing carbon material. For example,manipulating the processing variables of the intermediates as describedherein has a more important impact on the final carbon nanostructurethan the traditional methods of adjusting pyrolysis and activationvariables.

The ability to scale up a manufacturing approach as disclosed herein tomeet the high demand expected for the activated carbon materialsdisclosed herein has been demonstrated. Three parts of the process canbe identified: 1) ultrapure polymerization from precursor ultrapurepolymer materials; 2) freeze drying; and 3) pyrolysis/activation. In oneembodiment, each of these steps may be scaled employing standardmanufacturing equipment of three existing industries, for example,specialty chemical companies working with adhesives and epoxies;pharmaceutical and food related freeze drying providers; andmanufactures of low grade activated carbon, respectively.

It has been shown that the amount of catalyst and percentage of water inthe initial sol has a significant impact on the final performance of theactivated carbon material (e.g. when used in a supercapacitor). Thelarge number of process variables and the interaction between thesevariables enables continuous refinement of the process and allows forsome control over the final carbon structure. Accordingly, in oneembodiment, the present disclosure provides refinement of the processvariables. The disclosed refinements result in an ability to exertcontrol over the final carbon structure in a manner that was previouslyunobtainable.

The most common approach to refining process variables used in the artis to hold all but one variable constant and determine the effect ofvarying that one parameter. Alternately, and as described herein, thecombination of statistical analysis methods, DFE Pro Software, and afactorial design of experiments approach, were used to systematicallyvary multiple parameters simultaneously to obtain an optimized processfor preparing activated carbon material. By using this approach, theimpact of each of these variables on a range of different metrics (e.g.surface area, density, pore volume, etc.) related to the activatedcarbon material's structure are evaluated. When the ultrapure syntheticactivated carbon material is employed in a supercapacitor, additionalperformance metrics may be evaluated. For example, capacitance, densityand power density may be evaluated.

C. Characterization of Ultrapure Polymer Gels and Ultrapure SyntheticCarbon Materials

The structural properties of the final ultrapure synthetic activatedcarbon material, ultrapure synthetic activated amorphous carbonmaterial, \dried polymer gels, and the pyrolyzed, but unactivatedultrapure polymer gels may be measured using Nitrogen sorption at 17K, amethod known to those of skill in the art. The final performance andcharacteristics of the finished ultrapure synthetic activated carbonmaterial is important, but the intermediate products (both driedultrapure polymer gel and pyrolyzed, but not activated, ultrapurepolymer gel), can also be evaluated, particularly from a quality controlstandpoint, as known to those of skill in the art. The MicromereticsASAP 2020 is used to perform detailed micropore and mesopore analysis,which reveals the pore size distribution from 0.35 nm to 50 nm. Thesystem produces a nitrogen isotherm starting at a pressure of 10⁻⁷ atm,which enables high resolution pore size distributions in the sub 1 nmrange. The software generated reports utilize a Density FunctionalTheory (DFT) method to calculate properties such as pore sizedistributions, surface area distributions, total surface area, totalpore volume, and pore volume within certain pore size ranges.

In some embodiments, the pyrolyzed ultrapure polymer gels have a surfacearea from about 100 to about 1200 m²/g. In other embodiments, thepyrolyzed ultrapure polymer gels have a surface area from about 500 toabout 800 m²/g. In other embodiments, the pyrolyzed ultrapure polymergels have a surface area from about 500 to about 600 m²/g.

In some embodiments, the pyrolyzed ultrapure polymer gels have a tapdensity from about 0.1 to about 1.0 cc/g. In other embodiments, thepyrolyzed ultrapure polymer gels have a tap density from about 0.3 toabout 0.6 cc/g. In other embodiments, the pyrolyzed ultrapure polymergels have a tap density from about 0.35 to about 0.45 cc/g.

D. Tuning the Pore Size and Other Properties of Ultrapure Polymer Gels

The disclosed ultrapure carbon materials synthesized from synthetic,well-characterized precursors are different from activated carbon fromnatural sources such as coal, pitch, coconuts, etc. This is due in partto the fact that they can be tuned in both micropore and mesoporestructure and chemistry by carefully predesigned and executed processingcontrols. Additionally, an ultrapure carbon material as described hereincan contain a porous structure which can be optimized for a givenapplication (e.g. when used in a supercapacitor or other energy storagedevice). With the ability to tune the carbon nanostructure, performanceexceeding current performance data from traditional activated carbons isattained. Important variables include large accessible surface area,short micropores for electrolytic salt diffusion, and minimization ofwasted pore volume to enhance specific capacitance.

Manipulation of the process variables allows production of ultrapuresynthetic activated carbon materials that have properties which suit thedesired application. Accordingly, in one embodiment a method ofoptimizing the process variables for production of ultrapure polymergels, dried ultrapure polymer gels, pyrolyzed ultrapure polymer gels andultrapure synthetic activated carbon materials is provided. One approachfor optimization of process parameters comprises a design of experimentsstrategy. Using this strategy, the influence of multiple processvariables (e.g. up to 8 variables) can be studied with relatively fewexperiments. The data obtained from the design of experiments can beused to manipulate process variables to obtain specific properties inthe ultrapure polymer gels, dried ultrapure polymer gels, pyrolyzedultrapure polymer gels, and activated ultrapure polymer cryogels. Forexample, in some embodiments, the process parameters which aremanipulated to obtain the desired product characteristics are selectedfrom: Resorcinol/Catalyst Ratio, Resorcinol/Water Ratio, Particle Sizeat Freezing Step, Quench Temperature, Pyrolysis Time, PyrolysisTemperature, Activation Temperature, and Activation Time andcombinations thereof.

In some embodiments, a set of electrochemical test cells are utilizedwith a tetramethylammonium (TMA) cation. Whereas the tetraethylammonium(TEA) ion is 0.69 nm in diameter, the tetramethylammonium ion is only0.57 nm in diameter. Each cation is paired with a tetrafluoroborate(TFB) anion which is 0.46 nm in diameter. The sizes of these variousions shed some light on the pore size ranges described above. As long asmicropores are short and not tortuous, they admit ions smaller than thepore diameter. One way that capacitance and energy density are increasedis by allowing ions into as many pores as possible in the carbonnetwork. For example, pores smaller than 0.5 nm admit the TFB anion, butneither of the TEA or TMA cations. Pores between 0.5 nm and 0.65 nmadmit TMA cations but not TEA and pores larger than 0.65 nm will admitTEA ions. This concept summarizes the ion sieving theory, where thecarbon material is considered a sieve that will only allow ions smallerthan the pore size. Evaluation of the difference in capacitance andconsequently energy density developed on the anodes and cathodes ofcells containing TMATFB vs. TEATFB electrolytes provides insight intothe importance of pores volume within certain pore size range.

Manipulation of the process variables allows production of ultrapuresynthetic activated carbons that have a pore size distribution thatsuits the chosen electrolyte system. For example a carbon anode may beproduced that has a micropore peak at around 0.8 nm, which is centeredon a pore size that fits a TEA ion. Based on the output of the DFE ProSoftware, process settings are selected based on those variables thatare the most statistically significant for pores having pore volume andsurface area between 0.7-1.0 nm set as the primary performance metrics.Interaction of variables and multi-variable ‘contour maps’ are used toextrapolate process settings that lie either in between the settingsused above or outside the range specified above. After determining thetargeted process variables for meeting the pore size requirement of thistask, batch of ultrapure synthetic activated carbon, such as activatedcarbon cryogels, are produced based using these settings. The anodematerial is then characterized using the ASAP 2020 and DensityFunctional Theory for pore size distribution analysis to confirm theexistence of a high volume and surface area peak within the prescribedrange of 0.7-1.0 nm.

Analogously, a different pore size range, 0.6-0.8 nm, is used as thetarget for tuning the pore size for TMA cations, while still using thesame approach described herein. Still further, the approach can be usedto produce carbons that have a pore size distribution, less than 0.6 nm,that corresponds to TFB anions.

Varying the capacitance developed per gram of carbon in the anode andcathode enables production of a charge-balanced cell with a matchedcapacity for anions and cations. This approach improves the energydensity of the overall cell while reducing cost associated with creatingpores that are not right sized for the ions of the electrolyte.

In addition, according to the methods disclosed herein, carbons can bemass-produced with a targeted pore size distribution for any number ofelectrolyte ions. The ranges of pore sizes described herein were chosenfor the particular systems studied, however, other ranges can beproduced according to the methods disclosed herein. For example, datacan be extracted from the ASAP 2020 software generated reports and theDFE Pro Design of experiments can be altered to display the propertuning parameters for pores of any size. While particular parameters maynot have been disclosed herein, the factorial design of experimentsapproach enables one of skill in the art to make adjustments to generatethe targeted peak pore size.

Analysis of these results provides a number of different insights.Studying the ability of an anode or cathode with a known micropore sizepeak to develop maximum capacitance using a salt ion of known dimensionsprovides information on the effective size of the ions in play and whatpore size sieves out which ions. Use of the pore volume data as well asthe capacitance data of the systems disclosed herein providesidentification of the minimum pore size needed to develop capacitancewith a larger tetraethylammonium cation vs. the smallertetramethylammonium cation or a tetrafluoroborate anion. One targetedcarbon material for use as an electrode is a system where the microporepeak is just above the threshold when pores are too small to allow anion to electrosorb to the surface of the pore wall, while at the sametime minimizing pore volume in other ranges.

The factorial design of experiments approach, when used with pore volumein a specific range as a performance metric, indicates how to adjust theprocess parameters to maximize pore volume in that pore size range.

When electrolyte ions are free in an unconstrained solvent in theabsence of electric field, they are typically surrounded by solvent ionswhich serve to balance their charge. It is expected that this stilltakes place to some degree despite the strong electric field and thecramped space inside the pores. Each ion has a different propensitytowards keeping itself solvated and hence has a different effectivesize—larger for strong solvation and smaller for weak solvation. The ionsieving study described above evaluates the degree to which these saltsremain solvated and hence what size pores are appropriate.

As mentioned above, one way to maximize the energy density of ananostructured carbon electrode is to produce pores of the right sizefor the ions electrosorbed to the surface of that electrode. Anactivated carbon with a pore size distribution that is ideal for theanion and another that is ideal for the cation are assembled in anasymmetric cell capable of exceeding the capacitance and energy densityof symmetric cells used elsewhere.

E. Use of Dried Ultrapure Polymer Gels and Ultrapure Synthetic CarbonMaterial

The ultrapure synthetic carbon materials, for example, ultrapuresynthetic amorphous carbon materials can be used in devices requiringstable, high surface area micro- and mesoporous structure. Examples ofapplications for the disclosed carbon materials include, but are notlimited to: energy storage and distribution devices, ultracapacitorelectrodes, pseudocapacitor electrodes, battery electrodes, lead acidbattery electrodes, gas diffusion electrodes, including lithium-airelectrodes and zinc-air electrodes, lithium ion batteries and capacitors(for example as cathode material), conducting currentcollectors/scaffolds for other active materials in electrochemicalsystems, nanostructured material support scaffolds, solid state gasstorage (e.g., H₂ and CH₄ storage), capacitive deionization of saltwater, biomedical applications including poison control and controlleddrug release, air filtration, water filtration, chemical filtration,catalytic converters, thermal insulation, chromatographic packing,adsorbants and as a carbon-based scaffold support structure for othercatalytic functions such as hydrogen storage or fuel cell electrodes.

The disclosed carbon materials may also be employed in kinetic energyharvesting applications such as: hybrid electric vehicles, heavyhybrids, all electric drive vehicles, cranes, forklifts, elevators,electric rail, hybrid locomotives and electric bicycles. The ultrapuresynthetic amorphous carbon materials may also be employed in electricalback-up applications such as: UPS, data center bridge power, voltage dipcompensation, electric brake actuators, electric door actuators,electronics, telecom tower bridge power. Applications requiring pulsepower in which the ultrapure synthetic activated carbons of thisdisclosure may be useful include, but are not limited to: boardnetstabilization, electronics including cell phones, PDAs, camera flashes,electronic toys, wind turbine blade pitch actuators, power quality/powerconditioning/frequency regulation, electric supercharger. Yet other usesof the ultrapure synthetic amorphous carbon materials includes use inautomotive starting and stopping systems, power tools, flashlights,personal electronics, self contained solar powered lighting systems,RFID chips and systems, windfield developers for survey device power,sensors, pulse laser systems and phasers.

The disclosed carbon materials may also be used in applications wherehigh purity is critical, for example, applications in the medical,electronic, chemical analysis, mems (micromachines), and biologicalfields. Chemical and electrochemical sensors or detectors of all kindswould experience less interference from impurities or experience fewerside reactions caused or catalyzed by impurities. Examples areimpurities in air (explosives, hazardous chemicals, synthetic noses, orimpurities in water such as organics or water impurities in organicliquids.

The acid/base nature of carbon is largely a function of impuritiesincluding chemisorbed oxygen. Thus, the ultrapure synthetic amorphouscarbon materials are useful in applications where controlling theacid/base nature of the carbon material is desired.

Carbon is used as a reactant in the chemical production of materials andas an electrode in the electrochemical production of materials. Thus,the disclosed carbon materials find utility in the chemical andelectrochemical production of high purity materials especially metals.The disclosed carbon material may also be employed as an electrode inzinc-manganese oxide batteries (common flashlight batteries) andzinc-halogen batteries and incorporated into carbon-ultrapure polymercomposites for use as electrically conductive adhesives and seals andfor minimizing radiation leakage.

The dried ultrapure polymer gels disclosed herein find utility in anynumber of applications. For example, the dried ultrapure polymer gelsare useful as wood adhesives (e.g., for plywood or particle board),bonding textiles and metals to rubber (e.g., rubber tires), filtrationmedia, dielectric insulation, thermal insulation and as a resin incomposite materials (e.g., fiber glass and carbon fiber, etc.)

1. Ultracapacitor Devices

EDLCs use electrodes immersed in an electrolyte solution as their energystorage element. Typically, a porous separator immersed in andimpregnated with the electrolyte ensures that the electrodes do not comein contact with each other, preventing electronic current flow directlybetween the electrodes. At the same time, the porous separator allowsionic currents to flow through the electrolyte between the electrodes inboth directions thus forming double layers of charges at the interfacesbetween the electrodes and the electrolyte.

When electric potential is applied between a pair of electrodes of anEDLC, ions that exist within the electrolyte are attracted to thesurfaces of the oppositely-charged electrodes, and migrate towards theelectrodes. A layer of oppositely-charged ions is thus created andmaintained near each electrode surface. Electrical energy is stored inthe charge separation layers between these ionic layers and the chargelayers of the corresponding electrode surfaces. In fact, the chargeseparation layers behave essentially as electrostatic capacitors.Electrostatic energy can also be stored in the EDLCS through orientationand alignment of molecules of the electrolytic solution under influenceof the electric field induced by the potential. This mode of energystorage, however, is secondary.

EDLCS comprising the ultrapure synthetic carbon material, for exampleultrapure synthetic amorphous carbon material, can be employed invarious electronic devices where high power is desired. Accordingly, inone embodiment an electrode comprising ultrapure synthetic carbonmaterials is provided. In another embodiment an electrode comprisingultrapure synthetic amorphous carbon materials is provided. In a furtherembodiment, the electrode comprises ultrapure synthetic activated carbonmaterial, for example ultrapure synthetic activated amorphous carbonmaterial. In a further embodiment, an ultracapacitor comprising anelectrode comprising ultrapure synthetic carbon materials is provided.In a further embodiment of the foregoing, the ultrapure synthetic carbonmaterial is an ultrapure synthetic amorphous carbon material, forexample, an ultrapure synthetic activated amorphous carbon material.

The disclosed carbon materials find utility in any number of electronicdevices, for example wireless consumer and commercial devices such asdigital still cameras, notebook PCs, medical devices, location trackingdevices, automotive devices, compact flash devices, mobiles phones,PCMCIA cards, handheld devices, and digital music players.Ultracapacitors are also employed in heavy equipment such as: excavatorsand other earth moving equipment, forklifts, garbage trucks, cranes forports and construction and transportation systems such as buses,automobiles and trains.

In one embodiment, an ultracapacitor device comprising the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a gravimetric power of at least 10 W/g, at least 15W/g, at least 20 W/g, at least 25 W/g, at least 30 W/g or at least 35W/g. In another embodiment, an ultracapacitor device comprising theultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material comprises a volumetric power of at least 5 W/cc, atleast 10 W/cc, at least 15 W/cc or at least 20 W/cc. In anotherembodiment, an ultracapacitor device comprising the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon materialcomprises a gravimetric energy of at least 2.5 Wh/kg, at least 5.0Wh/kg, at least 7.5 Wh/kg, at least 10 Wh/kg, at least 12.5 Wh/kg, atleast 15.0 Wh/kg, at least 17.5. Wh/kg, at least 20.0 Wh/kg, at least22.5 wh/kg or at least 25.0 Wh/kg. In another embodiment, anultracapacitor device comprising the ultrapure synthetic activatedcarbon comprises a volumetric energy of at least 1.5 Wh/liter, at least3.0 Wh/liter, at least 5.0 Wh/liter, at least 7.5 Wh/liter, at least10.0 Wh/liter, at least 12.5 Wh/liter, at least 15 Wh/liter, at least17.5 Wh/liter or at least 20.0 Wh/liter.

In some embodiments of the foregoing, the gravimetric power, volumetricpower, gravimetric energy and volumetric energy of an ultracapacitordevice comprising the ultrapure synthetic carbon material or ultrapuresynthetic amorphous carbon material are measured by constant currentdischarge from 2.7 V to 1.89 V employing a 1.0 M solution oftetraethylammonium-tetrafluororoborate in acetonitrile (1.0 M TEATFB inAN) electrolyte and a 0.5 second time constant.

In one embodiment, an ultracapacitor device comprising the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a gravimetric power of at least 25 W/g, a volumetricpower of at least 10.0 W/cc, a gravimetric energy of at least 5.0 Wh/kgand a volumetric energy of at least 3.0 Wh/L.

In another embodiment, an ultracapacitor device comprising the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a gravimetric power of at least 15 W/g, a volumetricpower of at least 10.0 W/cc, a gravimetric energy of at least 20.0 Wh/kgand a volumetric energy of at least 12.5 Wh/L.

In one embodiment, an ultracapacitor device comprising the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a gravimetric capacitance of at least 15 F/g, atleast 20 F/g, at least 25 F/g, at least 30 F/g or at least 35 F/g. Inanother embodiment, an ultracapacitor device comprising the ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial comprises a volumetric capacitance of at least 10 F/cc, atleast 15 F/cc, at least 18 F/cc, at least 20 F/cc, at least 22 F/cc orat least 25 F/cc. In some embodiments of the foregoing, the gravimetriccapacitance and volumetric capacitance are measured by constant currentdischarge from 2.7 V to 0.1 V with a 5-second time constant andemploying a 1.8 M solution of tetraethylammonium-tetrafluororoborate inacetonitrile (1.8 M TEATFB in AN) electrolyte and a current density of0.5 A/g, 1.0 A/g, 4.0 A/g or 8.0 A/g.

In one embodiment, the present disclosure provides ultracapacitorscomprising an ultrapure synthetic carbon material or ultrapure syntheticamorphous carbon material as disclosed herein, wherein the percentdecrease in original capacitance (i.e., capacitance before beingsubjected to voltage hold) of the ultracapacitor comprising an ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial after a voltage hold period is less than the percent decreasein original capacitance of an ultracapacitor comprising known carbonmaterials. In one embodiment, the percent of original capacitanceremaining for an ultracapacitor comprising an ultrapure synthetic carbonmaterial or ultrapure synthetic amorphous carbon material after avoltage hold at 2.7 V for 24 hours at 65° C. is at least 90%, at least80%, at least 70%, at least 60%, at least 50%, at least 40%, at least30% at least 20% or at least 10%. In further embodiments of theforegoing, the percent of original capacitance remaining after thevoltage hold period is measured at a current density of 0.5 A/g, 1 A/g,4 A/g or 8 A/g.

In another embodiment, the present disclosure provides ultracapacitorscomprising an ultrapure synthetic carbon material or ultrapure syntheticamorphous carbon material as disclosed herein, wherein the percentdecrease in original capacitance of the ultracapacitor comprising anultrapure synthetic carbon material or ultrapure synthetic amorphouscarbon material after repeated voltage cycling is less than the percentdecrease in original capacitance of an ultracapacitor comprising knowncarbon materials subjected to the same conditions. For example, in oneembodiment, the percent of original capacitance remaining for anultracapacitor comprising an ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material is more than the percentof original capacitance remaining for an ultracapacitor comprising knowncarbon materials after 1000, 2000, 4000, 6000, 8000, or 1000 voltagecycling events comprising cycling between 2 V and 1V at a currentdensity of 4 A/g. In another embodiment, the percent of originalcapacitance remaining for an ultracapacitor comprising an ultrapuresynthetic carbon material or ultrapure synthetic amorphous carbonmaterial after 1000, 2000, 4000, 6000, 8000, or 1000 voltage cyclingevents comprising cycling between 2 V and 1V at a current density of 4A/g, is at least 90%, at least 80%, at least 70%, at least 60%, at least50%, at least 40%, at least 30% at least 20% or at least 10%.

As noted above, the ultrapure synthetic carbon material and ultrapuresynthetic amorphous carbon material can be incorporated intoultracapacitor devices. In some embodiments, the ultrapure syntheticcarbon material or ultrapure synthetic amorphous carbon material aremilled to an average particle size of about 10 microns using a Labomilljetmill operating in a nitrogen atmosphere. While not wishing to beboundby theory, it is believed that this fine particle size enhancesparticle-to-particle conductivity, as well as enabling the production ofvery thin sheet electrodes. The jetmill essentially grinds the carbonagainst itself by spinning it inside a disc shaped chamber propelled byhigh-pressure nitrogen. As the larger particles are fed in, thecentrifugal force pushes them to the outside of the chamber; as theygrind against each other, the particles migrate towards the center wherethey eventually exit the grinding chamber once they have reached theappropriate dimensions.

In further embodiments, after jet milling the carbon is blended with afibrous Teflon binder (3% by weight) to hold the particles together in asheet. The carbon Teflon mixture is kneaded until a uniform consistencyis reached. Then the mixture is rolled into sheets using a high-pressureroller-former that results in a final thickness of 50 microns. Theseelectrodes are punched into discs and heated to 195° C. under a dryargon atmosphere to remove water and/or other airbourne contaminants.The electrodes are weighed and their dimensions measured using calipers.

The carbon electrodes of the EDLCs are wetted with an appropriateelectrolyte solution. Examples of solvents for use in electrolytesolutions for use in the devices of the present application include butare not limited to propylene carbonate, ethylene carbonate, butylenecarbonate, dimethyl carbonate, methyl ethyl carbonate, diethylcarbonate, sulfolane, methylsulfolane and acetonitrile. Such solventsare generally mixed with solute, including, tetralkylammonium salts suchas TEATFB (tetraethylammonium tetrafluoroborate); TEMATFB(tri-ethyl,methylammonium tetrafluoroborate); EMITFB(1-ethyl-3-methylimidazolium tetrafluoroborate), tetramethylammonium ortriethylammonium based salts. Further the electrolyte can be a waterbased acid or base electrolyte such as mild sulfuric acid or potassiumhydroxide.

In some embodiments, the electrodes are wetted with a 1.0 M solution oftetraethylammonium-tetrafluororoborate in acetonitrile (1.0 M TEATFB inAN) electrolyte. In other embodiments, the electrodes are wetted with a1.0 M solution of tetraethylammonium-tetrafluororoborate in propylenecarbonate (1.0 M TEATFB in PC) electrolyte. These are commonelectrolytes used in both research and industry and are consideredstandards for assessing device performance. In other embodiments, thesymmetric carbon-carbon (C—C) capacitors are assembled under an inertatmosphere, for example, in an Argon glove box, and a NKK porousmembrane 30 micron thick serves as the separator. Once assembled, thesamples may be soaked in the electrolyte for 20 minutes or moredepending on the porosity of the sample.

In some embodiments, the capacitance and power output are measured usingcyclic voltametry (CV), chronopotentiometry (CP) and impedancespectroscopy at various voltages (ranging from 1.0-2.5 V maximumvoltage) and current levels (from 1-10 mA) on an Biologic VMP3electrochemical workstation. In this embodiment, the capacitance may becalculated from the discharge curve of the potentiogram using theformula:

$\begin{matrix}{C = \frac{I \times \Delta\; t}{\Delta\; V}} & {{Equation}\mspace{14mu} 1}\end{matrix}$where I is the current (A) and ΔV is the voltage drop, Δt is the timedifference. Because in this embodiment the test capacitor is a symmetriccarbon-carbon (C—C) electrode, the specific capacitance is determinedfrom:C _(s)=2C/m _(e)  Equation 2where m_(e) is the mass of a single electrode. The specific energy andpower may be determined using:

$\begin{matrix}{E_{s} = {\frac{1}{4}\frac{{CV}_{\max}^{2}}{m_{e}}}} & {{Equation}\mspace{14mu} 3} \\{P_{s} = {{E_{s}/4}\;{ESR}}} & {{Equation}\mspace{14mu} 4}\end{matrix}$where C is the measured capacitance V_(max) is the maximum test voltageand ESR is the equivalent series resistance obtained from the voltagedrop at the beginning of the discharge. ESR can alternately be derivedfrom impedance spectroscopy.

2. Batteries

The disclosed carbon materials also find utility as electrodes in a nuynumber of types of batteries. One such battery is the metal air battery,for example lithium air batteries. Lithium air batteries generallycomprise an electrolyte interposed between positive electrode andnegative electrodes. The positive electrode generally comprises alithium compound such as lithium oxide or lithium peroxide and serves tooxidize or reduces oxygen. The negative electrode generally comprises acarbonaceous substance which absorbs and releases lithium ions. As withsupercapacitors, batteries such as lithium air batteries which comprisehigher purity carbon materials are expected to be superior to batteriescomprising known carbon materials. Accordingly, in one embodiment thepresent invention provides a metal air battery, for example a lithiumair battery, comprising an ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material as disclosed herein.

Any number of other batteries, for example, zinc-carbon batteries,lithium/carbon batteries, lead acid batteries and the like are alsoexpected to perform better with higher purity carbon materials. Oneskilled in the art will recognize other specific types of carboncontaining batteries which will benefit from higher purity carbon.Accordingly, in another embodiment the present invention provides abattery, in particular a zinc/carbon, a lithium/carbon batteries or alead acid battery comprising an ultrapure synthetic carbon material orultrapure synthetic amorphous carbon material as disclosed herein.

EXAMPLES

The ultrapure polymer gels, cryogels, pyrolyzed cryogels, and ultrapuresynthetic amorphous carbon materials disclosed in the following Exampleswere prepared according to the methods disclosed herein. Chemicals wereobtained from commercial sources at reagent grade purity or better andwere used as received from the supplier without further purification.

Unless indicated otherwise, the following conditions were generallyemployed. Phenolic compound and aldehyde were reacted in the presence ofa catalyst in a binary solvent system. The molar ratio of phenoliccompound to aldehyde was typically 0.5 to 1. The reaction was allowed toincubate in a sealed glass ampoule at 90° C. for at least 24 hours oruntil gelation was complete. The resulting ultrapure polymer hydrogelcontained water, but no organic solvent; and was not subjected tosolvent exchange of water for an organic solvent, such as t-butanol. Theultrapure polymer hydrogel monolith was then physically disrupted, forexample by milling, to form ultrapure polymer hydrogel particles havingan average diameter of less than about 30 mm. Unless stated otherwise,the particles were then rapidly frozen, generally by immersion in a coldfluid (e.g. liquid nitrogen or ethanol/dry ice) and lyophilized.Generally, the lyophilizer shelf was pre-cooled to −50° C. beforeloading a tray containing the frozen ultrapure polymer hydrogelparticles on the lyophilizer shelf. The chamber pressure forlyophilization was typically in the range of 50 to 1000 mTorr and theshelf temperature was in the range of +10 to +25° C. Alternatively, theshelf temperature can be set lower, for example in the range of 0 to+10° C. Alternatively, the shelf temperature can be set higher, forexample in the range of 25 to +40° C.

The dried ultrapure polymer hydrogel was typically pyrolyzed by heatingin a nitrogen atmosphere at temperatures ranging from 800-1200° C. for aperiod of time as specified in the examples. Activation conditionsgenerally comprised heating a pyrolyzed ultrapure polymer hydrogel in aCO₂ atmosphere at temperatures ranging from 900-1000° C. for a period oftime as specified in the examples. Specific pyrolysis and activationconditions were as described in the following examples.

Example 1 Production of RF Gels from 100% Acetic Acid Solution

A series of RF gels were made form “neat” acetic acid (i.e., anhydrous).Three samples were produced with varying levels of ammonium carbonate(as “catalyst”): none, and ˜100 and ˜25 R/C. These samples were crushedby hand to create particles, frozen by immersion in liquid nitrogen, andlyophilized. A summary of these formulations and their specific surfaceareas is presented in Table 1. All three samples were monolithic andorange in color. Color intensity was greater for those samplescontaining ammonium carbonate. The specific surface area of the threesamples were between 597 and 644 m²/g.

FIG. 1 presents the incremental pore volume vs. pore width for thesesamples. The sample prepared without catalyst had a DFT average poresize of about 185 Å, with a broad peak between about 100 and 1000 Å, anda secondary peak at about 14 Å (and was relatively devoid of pore volumein between). In contrast, as catalyst was added the main broad peakdemonstrated a shift in the distribution towards lower pore widths(there was also a secondary peak at about 12 to 16 Å). The DFT averagepore size for samples containing about 100 and about 25 R/C ammoniumcarbonate were about 78 Å and 45 Å, respectively. Interestingly, theselatter samples were relatively devoid of pores above 300 Å.

TABLE 1 Summary of gels produced from 100% acetic acid solution (nowater added prior to addition of formaldeyde) Final Gelling Dried GelSpecific Sample R/S R/C pH conditions Surface Area (m²/g) 003-113-2 0.3∞ 2.0 O/N @ 90° C. 644 003-113-3 0.3 95 1.9 597 003-113-4 0.3 25 2.1 605Abbreviations: R/S = ratio of resorcinol to solvent (in g/mL); R/C =ratio of resocorcinol to catalyst (in g/g); O/N = overnight, typicallyabout 18 hours.

Example 2 Production of RF Gels from 90:10 Acetic Acid:Water (vol:vol)Solution

In order to examine the effect of addition of a small amount of water inthe system, a series of RF gels were produced from a mixed solvent ofacetic acid:water in a 90:10 vol:vol ratio (prior to addition offormaldehyde). Three samples were produced with varying levels ofammonium carbonate: none, and ˜100 and ˜25 R/C. These samples werecrushed by hand to create particles, frozen by immersion in liquidnitrogen, and lyophilized.

A summary of these formulations and their specific surface areas arepresented in Table 2. All three samples were monolithic and orange incolor. Color intensity was greater for those samples containing ammoniumcarbonate. The specific surface area of the three samples was between586 and 653 m2/g.

FIG. 2 presents the incremental pore volume vs. pore width for thesesamples. The sample prepared without catalyst had a DFT average poresize of about 160 Å, with a broad peak between about 100 and 1000 Å, andsecondary peaks at about 11 Å and 13 Å (and was relatively devoid ofpore volume in between). In contrast, as catalyst was added the mainbroad peak demonstrated a shift in the distribution towards lower porewidths (there were also secondary peaks over the range of about 12 Å to15 Å). The DFT average pore size for samples containing about 100 andabout 25 R/C ammonium carbonate were about 59 Å and 39 Å, respectively.Overall, the trends for the 90:10 acetic acid:water samples were similarto those observed for the case where the resorcinol was initiallydissolved in 100% acetic acid discussed above.

TABLE 2 Summary of RF gels produced from 50:50 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde) Final GellingDried Gel Specific Sample R/S R/C pH conditions Surface Area (m²/g)003-113-6 0.3 ∞ 1.3 O/N @ 90° C. 653 003-113-7 0.3 100 1.9 599 003-113-80.3 25 2.1 586 Abbreviations: R/S = ratio of resorcinol to solvent (ing/mL); R/C = ratio of resocorcinol to catalyst (in g/g); O/N =overnight, typically about 18 hours.

Example 3 Production of RF Gels from 50:50 Acetic Acid:Water (vol:vol)Solution

To further examine the effect of addition of water, a series of RF gelswere produced from 50:50 acetic acid:water (prior to addition offormaldehyde). Three samples were produced with varying levels ofammonium carbonate: none, and ˜100 and ˜25 R/C. A fourth sample was madewith the addition of ammonium acetate at a ratio of ˜25 R/C. Thesesamples were crushed by hand to create particles, frozen by immersion inliquid nitrogen, and lyophilized.

A summary of these formulations and their specific surface areas arepresented in Table 3. All four samples were monolithic and orange incolor. Color intensity was greater for those samples containing ammoniumcarbonate or ammonium acetate. The specific surface area of the foursamples was between 560 and 693 m²/g.

FIG. 3 presents the incremental pore volume vs. pore width for thesesamples. The sample prepared without catalyst had a DFT average poresize of about 193 Å, with a broad peak between about 100 and 1000 Å, anda secondary peak at about 14 Å (and was relatively devoid of pore volumein between). In contrast, as catalyst was added, the main broad peakdemonstrated a shift in the distribution towards lower pore widths(there was also a secondary peak at about 10 Å to 14 Å). The DFT averagepore size for samples containing about 100 and about 25 R/C ammoniumcarbonate were about 79 Å and 32 Å, respectively. The DFT average poresize for the sample containing about 25 R/C ammonium acetate was about33 Å. Overall, the trends for the 50:50 acetic acid:water samples weresimilar to those observed for the case where the resorcinol wasinitially dissolved in 100% acetic acid or 90:10 acetic acid:water asdiscussed above.

TABLE 3 Summary of RF gels produced from 50:50 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde) Final GellingDried Gel Specific Sample R/S R/C pH conditions Surface Area (m²/g)003-117-1 0.3 ∞ 1.4 O/N @ 90° C. 693 ± 27 003-117-2 0.3 95 2.0 663 ± 23003-117-3 0.3 25 2.5 600 ± 40 003-117-4 0.3 24 2.4 560 (Amm. Acetate)Abbreviations: R/S = ratio of resorcinol to solvent (in g/mL); R/C =ratio of resocorcinol to catalyst (in g/g); O/N = overnight, in thiscase additional samples were incubated for an additional day, resultingin a total time of about 36 h. Where specific surface areas are given asaverage and standard deviation, values are calculated from two datapoints.

Example 4 Production of RF Gels from 25:75 Acetic Acid:Water (vol:vol)Solution

The next system was comprised predominantly of water, specifically 25:75acetic acid:water (prior to addition of formaldehyde). Three sampleswere produced with varying levels of ammonium carbonate: none, and ˜100and ˜25 R/C. A fourth sample was made with the addition of ammoniumacetate at a ratio of ˜25 R/C. These samples were crushed by hand tocreate particles, frozen by immersion in liquid nitrogen, andlyophilized.

A summary of these formulations and their specific surface areas arepresented in Table 4. Additional samples that were produced withammonium acetate at lower R/C ratios of 10:1 and 1:1 are also includedin the table. Sample prepared in absence of catalyst was light orange incolor and after drying the cryogel had a specific surface area of about340 m²/g. Those samples containing ammonium carbonate or ammoniumacetate were darker in color (in particular for the 100 R/C samples) andalso appeared less cloudy in nature. However, sample produced at thehighest level of ammonium acetate, i.e., R/C 1:1 was very clay-like andwet in consistency, and exhibited an extremely low surface area.Compared to the cryogel in this series devoid of catalyst, thosecontaining either sodium carbonate or sodium acetate at R/C of 25:1 to100:1 had a much higher specific surface area of over 700 m²/g. Samplesprepared with ammonium acetate at R/C of 10 and 1 produced a lowersurface area of about 427 m²/g and 3.4 m²/g, respectively.

FIG. 4 presents the incremental pore volume vs. pore width for some ofthese samples. The sample prepared without catalyst had a broad peakbetween about 100 and over 1000 Å with substantial incremental porevolume above pore width of 1000 Å, and a secondary peak at about 13 Å,and a BHJ adsorption average pore width was 193 Å. Addition of about 100R/C ammonium carbonate shifted the distribution significantly, althoughthe DFT adsorption average pore size was similar to that observedwithout catalyst (about 200 Å). Samples containing about 25 R/C ammoniumcarbonate or ammonium acetate exhibited a shift in the distributiontowards lower pore widths, resulting in DFT average pore size of about92 Å and 104 Å, respectively. All samples exhibited peaks in incrementalpore volume over the pore width range of about 12 to 16 Å.

TABLE 4 Summary of RF gels produced from 25:75 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde) Final GellingDried Gel Specific Sample R/S R/C pH conditions Surface Area (m²/g)003-118-1 0.3 ∞ 2.3 O/N @ 90° C. 469 003-118-2 0.3 97 2.9 722 003-118-30.3 25 3.3 724 003-118-4 0.3 24 3.1 728 (Amm. acetate) 003-127-3 0.3 103.5 427 (Amm. Acetate) 003-127-4 0.3 1 3.9 3.4 (Amm. Acetate)Abbreviations: R/S = ratio of resorcinol to solvent (in g/mL); R/C =ratio of resorcinol to catalyst (in g/g); O/N = overnight, typicallyabout 18 hours.

Example 5 Production of RF Gels from 10:90 Acetic Acid:Water (vol:vol)Solution

An analogous series of samples was prepared at 10:90 acetic acid:water(prior to addition of formaldehyde). Three samples were produced withvarying levels of ammonium carbonate: none, and ˜100 and ˜25 R/C. Afourth sample was made with the addition of ammonium acetate at a ratioof ˜25 R/C. These samples were crushed by hand to create particles,frozen by immersion in liquid nitrogen, and lyophilized.

A summary of these formulations and their specific surface areas ispresented in Table 5. The sample prepared in this series withoutcatalyst was visually somewhat monolithic, but very clay-like and wet inconsistency, and very light orange color. Upon drying, the materialexhibited an extremely low surface area of <1 m²/g. Samples withammonium salts were darker in color, and appeared less cloudy. Thesesamples also exhibited a much higher specific surface area in thecryogel. In addition, there was a trend for increasing specific surfacearea for the higher levels of ammonium salts.

FIG. 5 presents the incremental pore volume vs. pore width for thesamples from this series that included an ammonium salt. Thedistribution for all three samples was similar, with a trend towards avery minor shifting in the distribution in the presence of higher amountof catalyst. Specifically, in the presence of ammonium carbonate R/C100:1, the BHJ adsorption average pore width was 338 Å, compared to 187Å and 201 Å in the presence of R/C 25:1 ammonium carbonate and ammoniumacetate, respectively.

TABLE 5 Summary of RF gels produced from 10:90 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde) Final GellingDried Gel Specific Sample R/S R/ C pH conditions Surface Area (m²/g)003-116-3 0.3 ∞ 2.2 O/N @ 90° C. 0.5 003-116-1 0.3 99 2.9 327 ± 10 003-116-2 0.3 25 3.6 429 03-116-4 0.3 24 3.2 539 ± 175 Abbreviations:R/S = ratio of resorcinol to solvent (in g/mL); R/C = ratio ofresocorcinol to catalyst (in g/g); O/N = overnight, typically about 18h.

Example 6 Production of RF Gels from 1:99 Acetic Acid:Water (vol:vol)Solution

Yet another, lower ratio of acetic acid to water was studied, namely1:99 (prior to addition of formaldehyde). Three samples were producedwith varying levels of ammonium carbonate: none, and ˜100 and ˜25 R/C. Afourth sample was made with the addition of ammonium acetate at a ratioof ˜25 R/C. These samples were crushed by hand to create particles,frozen by immersion in liquid nitrogen, and lyophilized.

A summary of these formulations and their specific surface areas ispresented in Table 6. All samples were clay-like and wet in consistency.The sample prepared without catalyst exhibited an extremely low surfacearea of 1.5 m²/g. Compared to samples produced at higher amounts ofacetic acid, samples in this series were generally light orange in colorand cloudy in nature. Samples where an ammonium salt was added exhibitedmoderately high specific surface area, in the range of 140 to 278 m²/g,but generally lower than values obtained for samples prepared at higheracetic acid content.

TABLE 6 Summary of RF gels produced from 1:99 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde) Final GellingDried Gel Specific Sample R/S R/C pH conditions Surface Area (m²/g)003-119-1 0.3 ∞ 2.9 O/N @ 90° C. 1.5 003-119-2 0.3 101 4.3 210 003-119-30.3 25 5.0 140 03-119-4 0.3 24 4.3 278 Abbreviations: R/S = ratio ofresorcinol to solvent (in g/mL); R/C = ratio of resocorcinol to catalyst(in g/g); O/N = overnight, typically about 18 hours.

Example 7 Relationship Between pH and Surface Characteristics forVarious RF Gels

A plot of specific surface area vs. pH for all samples is presented inFIG. 6. As can be seen, there was a general trend towards higherspecific surface area as pH decreases. However, notable exceptions arethe samples 003-116-3 and 003-119-1 (which are materials produced fromthe two lowest acetic acid contents studied and do not contain anyammonium salts), and sample 003-127-4 (which was produced from 25%acetic acid and the highest amount of ammonium acetate studied, R/C=1).A similar plot of pH vs. DFT adsorption average pore width does notreflect any discernable trend. Therefore, the pH alone does not appearto be a controlling variable for tuning pore width distribution in theRF ultrapure polymer gel, and must be considered along with the amount(and type) of catalyst added, in this case, basic ammonium salts,specifically carbonate or acetate.

Example 8 Production of RF Gels from 25:75 Acetic Acid: Water and RSRatio of 0.6

Table 7 presents data for RF ultrapure polymer gels that were producedfrom 25:75 acetic acid:water, and in this case, the RS is relativelyhigh, namely 0.6. Samples in this series were hard and monolithic andsamples with ammonium salts exhibited notably higher specific surfacearea (591 to 612 m²/g) compared to the corresponding ultrapure polymergel absent any ammonium salt (specific surface area of 271 m²/g).

TABLE 7 Summary of RF gels produced from 25:75 acetic acid:water(vol:vol) solution (prior to addition of formaldehyde), and RS = 0.6Final Gelling Dried Gel Specific Surface Sample R/S R/C pH conditionsArea (m²/g) 006-048-1 0.6 ∞ 2.9 72 h 271 006-048-2 0.6 100 3.6 @ 90° C.612 006-048-3 0.6 25 4.1 595 006-048-4 0.6 25 3.9 591 Abbreviations: R/S= ratio of resorcinol to solvent (in g/mL); R/C = ratio of resocorcinolto catalyst (in g/g).

Example 9 Pyrolysis of RF Ultrapure Polymer Gels

Eight samples from those discussed above were pyrolyzed. The details ofthese samples are provided in Table 8. All samples in the Table werepyrolyzed via incubation at 900° C. for a dwell time of 60 min. Theweight loss upon pyrolysis was 53±3%. In general, the specific surfacearea of the pyrolyzed gel was similar to that for the dried ultrapurepolymer gel before pyrolysis.

TABLE 8 Summary of pyrolyzed samples Pyrolyzed Gel Specific Dried GelSpecific Pyrolysis Weight Surface Area Sample Surface Area (m²/g) Loss(%) (m²/g) 003-116-4 PC  539 ± 179 56 743 003-117-1 PC 693 ± 27 57 697003-117-2 PC 663 ± 23 57 699 003-117-3 PC 600 ± 40 56 548 003-117-4 PC560 56 573 003-118-2 PC 722 52 705 ± 24 003-118-3 PC 724 52 702003-118-4 PC 728 51 689 ± 24

The pore size distribution in the pyrolyzed gel was related to that forthe dried ultrapure polymer gel before pyrolysis. Specifically, therewas a trend towards a shift in the incremental pore volume vs. porewidth towards lower pore widths. For example, FIG. 7 shows theincremental pore volume vs. pore width plot for sample 003-117-2 before(FIG. 7 A) and after (FIG. 7B) the pyrolysis. It can be seen that theoverall distribution was similar, with a slight shift towards lower porewidth after pyrolysis.

Further examples are provided in FIG. 8, FIG. 9, FIG. 10 and FIG. 11 forsamples 003-117-4, 003-118-2, 003-118-3, and 003-118-4, respectively. Ineach case, the pore width distribution in the pyrolyzed sample (FIGS.8B, 9B, 10B, and 11B) is reflective of the dried ultrapure polymer gelbefore pyrolysis (and slightly shifted downwards towards smaller porewidths) (FIGS. 8A, 9A, 10A, and 11A). These data are important inshowing that tunability in the dried ultrapure polymer gel is carriedover into tunability for the pyrolyzed material.

Example 10 Preparation of Ultrapure Synthetic Activated Carbon Materials

Ultrapure synthetic activated carbon material was prepared from thepyrolyzed samples. A summary of the ultrapure synthetic activatedcarbons produced is presented in Table 9. A plot of the percent weightloss during the activation process vs the specific surface area isdepicted in FIG. 12. As can be seen, there was a trend of increasingspecific surface area with increasing activation weight loss. There wasa trend observed that samples with high specific surface area in thepyrolyzed material tended to have a higher specific surface area in theactivated carbon for a given activation weight loss. These data showthat high specific surface area ultrapure synthetic activated carbonscan be produced from the ultrapure polymer gel formulations describedherein.

TABLE 9 Summary of activated carbon samples Activation Activated CarbonPyrolyzed Gel (Total) Specific Specific Surface Activation Weight LossSurface Area Sample Area (m²/g) Conditions (%) (m²/g) 003-116-4 AC 743 20 min 900° C. 13 910 003-116-4 AC2 110 min 900° C. 87 2895 003-117-1AC 697  90 min 900° C. 40 1565 003-117-3 AC 548  45 min 900° C. 38 1245003-117-3 AC2  90 min 900° C. 98 2906 003-117-4 AC 573  45 min 1000° C.41 1808 003-118-4 AC 689 ± 24 100 min 900° C. 25 1203 003-118-4 AC2  45min 1000° C. 83 2716

An example of the pore volume distribution for activated carbon producedfrom the RF ultrapure polymer gels described herein is presented in FIG.13. In this case, the ultrapure synthetic activated carbon, namely003-118-AC2 exhibits a pore volume distribution that is reflective ofthe pyrolyzed sample (see FIG. 11). These data are important in showingthat ability to tune pore and surface characteristics in the ultrapurepolymer gel will be translated to an ability to tune the characteristicsin the ultrapure synthetic pyrolyzed and ultrapure synthetic activatedcarbon materials produced from the ultrapure polymer gels.

Example 11 Preparation of Dried Ultrapure Polymer Gel

According to the methods disclosed herein a ultrapure polymer gel wasprepared from a binary solvent system comprised of water and acetic acid(75:25), resorcinol, formaldehyde, and ammonium acetate. The materialwas then placed at elevated temperature to allow for gellation to createa ultrapure polymer gel. Ultrapure polymer gel particles were createdfrom the ultrapure polymer gel and passed through a 4750 micron meshsieve, and said ultrapure polymer gel particles were frozen by immersionin liquid nitrogen, and loaded into a lyophilization tray at a loadingof 3 to 7 g/in², and lyophilized. The time to dry (as inferred from timefor product to reach within 2° C. of shelf temperature) was related tothe product loading on the lyophilizer shelf.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a Micromeritics Surface Area and Porosity Analyzer (modelTriStar II). The measured specific surface area using the BET approachwas in the range of about 500 to 700 m²/g.

Example 12 Production of Ultrapure Pyrolyzed Synthetic Carbon Materialfrom Dried Ultrapure Polymer Gel

The dried gel as described in Example 11 was pyrolyzed by passagethrough a rotary kiln (alumina tube with 3.75 in inner diameter) at 850°C. with a nitrogen gas flow of 200 L/h rate. The weight loss uponpyrolysis was about 52%.

The surface area of the pyrolyzed dried ultrapure polymer gel wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the standard BETapproach was in the range of about 600 to 700 m²/g.

Example 13 Production of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 12 wasactivated by multiple passes through a rotary kiln (alumina tube with2.75 in inner diameter) at 900° C. under a CO₂ flow rate of 30 L/min,resulting in a total weight loss of about 45%.

The surface area of the ultrapure synthetic activated carbon wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the BET approach wasin the range of about 1600 to 2000 m²/g.

Example 14 Micronization of Ultrapure Synthetic Activated Carbon Via JetMilling

The ultrapure synthetic activated carbon from Example 13 was jet milledusing a Jet Pulverizer Micron Master 2 inch diameter jet mill. Theconditions were about 0.7 lbs of ultrapure synthetic activated carbonper hour, nitrogen gas flow about 20 scf per min and about 100 psipressure. The average particle size after jet milling was about 8 to 10microns.

Example 15 Preparation of Dried Ultrapure Polymer Gel

According to the methods disclosed herein a ultrapure polymer gel wasprepared from a binary solvent system comprised of water and acetic acid(75:25), resorcinol, formaldehyde, and ammonium acetate. The materialwas then placed at elevated temperature to allow for gellation to createa ultrapure polymer gel. Ultrapure polymer gel particles were createdfrom the ultrapure polymer gel and passed through 4750 micron meshsieve, and said ultrapure polymer gel particles were frozen by immersionin liquid nitrogen, and loaded into a lyophilization tray at a loadingof 3 to 7 g/in², and lyophilized. The time to dry (as inferred from timefor product to reach within 2° C. of shelf temperature) was related tothe product loading on the lyophilizer shelf.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a Micromeritics Surface Area and Porosity Analyzer (modelTriStar II). The measured specific surface area using the BET approachwas in the range of about 500 to 700 m²/g.

Example 16 Production of Ultrapure Pyrolyzed Synthetic Carbon Materialfrom Dried Ultrapure Polymer Gel

The dried gel as described in Example 15 was pyrolyzed by passagethrough a rotary kiln (quartz tube with a 3.75 inch inner diameter) at850° C. with a nitrogen gas flow of 200 L/h rate. The weight loss uponpyrolysis was about 51%.

The surface area of the pyrolyzed dried ultrapure polymer gel wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the standard BETapproach was in the range of about 600 to 700 m²/g.

Example 17 Preparation of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 16 wasactivated by incubation at 900° C. in a silica tube (3.75 inch innerdiameter) with 6.7 L/min CO₂ flow rate, to achieve a final weight loss(compared to the starting pyrolyzed carbon) of about 54%.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a surface area and porosity analyzer. The measuredspecific surface area using the BET approach was in the range of about1600 to 2000 m²/g.

Example 18 Purity Analysis of Ultrapure Synthetic Activated Carbon &Comparison Carbons

The ultrapure synthetic activated carbon samples were examined for theirimpurity content via proton induced x-ray emission (PIXE). PIXE is anindustry-standard, highly sensitive and accurate measurement forsimultaneous elemental analysis by excitation of the atoms in a sampleto produce characteristic X-rays which are detected and theirintensities identified and quantitated. PIXE is capable of detection ofall elements with atomic numbers ranging from 11 to 92 (i.e., fromsodium to uranium).

The PIXE impurity (Imp.) data for ultrapure synthetic activated carbonsas disclosed herein as well as other activated carbons for comparisonpurposes is presented in Table 10. Sample 1 is the ultrapure syntheticactivated carbon of Example 13, Sample 2 is the ultrapure syntheticmicronized activated carbon of Example 14, Sample 3 is the ultrapuresynthetic activated carbon of Example 17, Sample 4 is the ultrapuresynthetic activated carbon of Example 35, Sample 5 is the ultrapuresynthetic activated carbon of Example 38, Sample 6 is an activatedcarbon denoted “MSP-20” obtained from Kansai Coke and Chemicals Co.,Ltd. (Kakogawa, Japan), Sample 7 is an activated carbon denoted“YP-50F(YP-17D)” obtained from Kuraray Chemical Co. (Osaka, Japan).

As seen in Table 10, the ultrapure synthetic activated carbons accordingto the instant disclosure have a lower PIXE impurity content and lowerash content as compared to other known activated carbon samples.

TABLE 10 Purity Analysis of Ultrapure Synthetic Activated Carbon &Comparison Carbons Impurity Concentration (PPM) Impurity Sample 1 Sample2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 Na ND* ND ND ND ND353.100 ND Mg ND ND ND ND ND 139.000 ND Al ND ND ND ND ND 63.850 38.941Si 53.840 92.346 25.892 17.939 23.602 34.670 513.517 P ND ND ND ND ND ND59.852 S ND ND ND ND ND 90.110 113.504 Cl ND ND ND ND ND 28.230 9.126 KND ND ND ND ND 44.210 76.953 Ca 21.090 16.971 6.141 9.299 5.504 ND119.804 Cr ND ND ND ND ND 4.310 3.744 Mn ND ND ND ND ND ND 7.552 Fe7.582 5.360 1.898 2.642 1.392 3.115 59.212 Ni 4.011 3.389 0.565 ND ND36.620 2.831 Cu 16.270 15.951 ND ND ND 7.927 17.011 Zn 1.397 0.680 1.1801.130 0.942 ND 2.151 Total 104.190 134.697 35.676 31.010 31.44 805.1421024.198 (% Ash) (0.018) (0.025) (<0.007) (0.006) (0.006) (0.13) (0.16)*ND = not detected by PIXE analysis

Example 19 Electrochemical Performance of Ultrapure Synthetic ActivatedCarbon

The ultrapure synthetic activated carbon of Example 13 (i.e., Sample #1)was analyzed for its electrochemical performance, specifically for itsperformance as an electrode material in an EDLC. Specific detailsregarding fabrication of electrodes, EDLC, and their testing aredescribed below.

Capacitor electrodes comprised 99 parts by weight carbon particles(average particle size 5-15 microns) and 1 part by weight Teflon. Thecarbon and Teflon were masticated in a mortar and pestle until theTeflon was well distributed and the composite had some physicalintegrity. After mixing, the composite was rolled out into a flat sheet,approximately 50 microns thick. Electrode disks, approximately 1.59 cmin diameter, were punched out of the sheet. The electrodes were placedin a vacuum oven attached to a dry box and heated for 12 hours at 195°C. This removed water adsorbed from the atmosphere during electrodepreparation. After drying, the electrodes were allowed to cool to roomtemperature, the atmosphere in the oven was filled with argon and theelectrodes were moved into the dry box where the capacitors were made.

A carbon electrode was placed into a cavity formed by a 1 inch (2.54 cm)diameter carbon-coated aluminum foil disk and a 50 micron thickpolyethylene gasket ring which had been heat sealed to the aluminum. Asecond electrode was then prepared in the same way. Two drops ofelectrolyte comprising 1.8 M tetraethylene ammonium tetrafluoroborate inacetonitrile were added to each electrode. Each electrode was coveredwith a 0.825 inch diameter porous polypropylene separator. The twoelectrode halves were sandwiched together with the separators facingeach other and the entire structure was hot pressed together.

When complete, the capacitor was ready for electrical testing with apotentiostat/function generator/frequency response analyzer. Capacitancewas measured by a constant current discharge method, comprising applyinga current pulse for a known duration and measuring the resulting voltageprofile. By choosing a given time and ending voltage, the capacitancewas calculated from the following C=It/ΔV, where C=capacitance,I=current, t=time to reached the desired voltage and ΔV=the voltagedifference between the initial and final voltages. The specificcapacitance based on the weight and volume of the two carbon electrodeswas obtained by dividing the capacitance by the weight and volumerespectively. This data is reported in Table 11 for discharge between2.7 and 1.89V.

TABLE 11 Summary of capacitance performance parameters MeasuredCapacitance Performance Parameters Value Gravimetric Power* 13.1 W/gVolumetric Power* 8.7 W/cc Gravimetric Energy* 4.8 Wh/kg VolumetricEnergy* 3.2 Wh/liter Gravimetric Capacitance @ RC = 5** 22 F/gVolumetric Capacitance @ RC = 5** 15 F/cc Gravimetric Capacitance @ RC =20^(‡) 27 F/g Volumetric Capacitance @ RC = 20^(‡) 18 F/cc *By constantcurrent discharge from 2.7 to 1.89 volts with TEATFB in AN, 0.5 secondtime constant. **By constant current discharge from 2.7 to 0.1 V,5-second time constant. ^(‡)By constant current discharge from 2.7 to0.1 V, 20-second time constant.

Example 20 Preparation of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 12 wasactivated by incubation at 900° C. in a silica tube (3.75 inch innerdiameter) with 15 L/min CO₂ flow rate, to achieve a final weight loss(compared to the starting pyrolyzed carbon) of about 55%.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a surface area and porosity analyzer. The measuredspecific surface area using the BET approach was in the range of about2000 m²/g. The measured pore volume (Dv50) of the ultrapure syntheticactivated carbon was at a pore size of about 1.8 nm. The measured porevolume (Dv5) of the ultrapure synthetic activated carbon was at a poresize of about 0.5 nm. The measured total pore volume of the ultrapuresynthetic activated carbon was 1.42 cc/g.

Example 21 Micronization of Ultrapure Synthetic Activated Carbon

The ultrapure synthetic activated carbon from Example 20 was jet milledusing a Jet Pulverizer Micron Master 2 inch diameter jet mill. Theconditions were about 0.7 lbs of ultrapure synthetic activated carbonper hour, nitrogen gas flow about 20 scf per min and about 100 psipressure. The average particle size (Dv50) after jet milling was about 6microns. The Dv95 after jet milling was about 19 microns. The measuredtotal ash content of the ultrapure synthetic activated carbon was0.008%. The measured tap density of the ultrapure synthetic activatedcarbon was 0.22 g/cc.

Example 22 Electric Double Layer Capacitor Device Comprising UltrapureSynthetic Activated Carbon

The ultrapure synthetic activated carbon of Example 21 was used as anelectrode material for an electric double later capacitor device asdescribed below.

Capacitor electrodes comprised 99 parts by weight carbon particles(average particle size 5-15 microns) and 1 part by weight Teflon. Thecarbon and Teflon were masticated in a mortar and pestle until theTeflon was well distributed and the composite had some physicalintegrity. After mixing, the composite was rolled out into a flat sheet,approximately 50 microns thick. Electrode disks, approximately 1.59 cmin diameter, were punched out of the sheet. The electrodes were placedin a vacuum oven attached to a dry box and heated for 12 hours at 195°C. This removed water adsorbed from the atmosphere during electrodepreparation. After drying, the electrodes were allowed to cool to roomtemperature, the atmosphere in the oven was filled with argon and theelectrodes were moved into the dry box where the capacitors were made.

A carbon electrode was placed into a cavity formed by a 1 inch (2.54 cm)diameter carbon-coated aluminum foil disk and a 50 micron thickpolyethylene gasket ring which had been heat sealed to the aluminum. Asecond electrode was then prepared in the same way. Two drops ofelectrolyte comprising 1.8 M tetraethylene ammonium tetrafluoroborate inacetonitrile were added to each electrode. Each electrode was coveredwith a 0.825 inch diameter porous polypropylene separator. The twoelectrode halves were sandwiched together with the separators facingeach other and the entire structure was hot pressed together.

Example 23 Electrochemical Performance of an Electric Double LayerCapacitor Device Comprising Ultrapure Synthetic Activated Carbon

The device described in Example 22 was subjected to electrical testingwith a potentiostat/function generator/frequency response analyzer.Capacitance was measured by a constant current discharge method,comprising applying a current pulse for a known duration and measuringthe resulting voltage profile over time. By choosing a given time andending voltage, the capacitance was calculated from the followingC=It/ΔV, where C=capacitance, I=current, t=time to reached the desiredvoltage and ΔV=the voltage difference between the initial and finalvoltages. The specific capacitance based on the weight and volume of thetwo carbon electrodes was obtained by dividing the capacitance by theweight and volume respectively. This data is reported in Table 12 fordischarge between 2.7 and 1.89V.

TABLE 12 Capacitance Performance Parameters of an EDLC ComprisingUltrapure Synthetic Activated Carbon Measured Capacitance PerformanceParameters Value Gravimetric Power* 28.8 W/g Volumetric Power* 14.4 W/ccGravimetric Energy* 7.4 Wh/kg Volumetric Energy* 3.7 Wh/literGravimetric Capacitance @ RC = 5** 28 F/g Volumetric Capacitance @ RC =5** 14 F/cc Gravimetric Capacitance @ RC = 20^(‡) 29 F/g VolumetricCapacitance @ RC = 20^(‡) 14 F/cc *By constant current discharge from2.7 to 1.89 volts with TEATFB in AN, 0.5 second time constant. **Byconstant current discharge from 2.7 to 0.1 V, 5-second time constant.^(‡)By constant current discharge from 2.7 to 0.1 V, 20-second timeconstant.

Example 24 Electrochemical Performance of Electric Double LayerCapacitor Devices Comprising Commercially Available Activated Carbon

For comparison, devices were also constructed from two othercommercially available activated carbons: Sample #6 and Sample #7. Thegravimetric and volumetric power and gravimetric and volumetric energyperformance data for these comparator carbons are presented in Table 13for discharge between 2.7 and 1.89V.

TABLE 13 Capacitance Performance Parameters for Comparator CarbonsCapacitance Performance Measured Value Measured Value Parameters Sample6 Sample 7 Gravimetric Power* 11.2 W/g 7.7 W/g Volumetric Power*  7.2W/cc 6.2 W/cc Gravimetric Energy*  3.5 Wh/kg 3.0 Wh/kg VolumetricEnergy*  2.2 Wh/liter 2.4 Wh/liter *By constant current discharge from2.7 to 1.89 volts with TEATFB in acetonitrile (AN), 0.5 second timeconstant.

Example 25 Electrochemical Performance of Electric Double LayerCapacitor Devices Comprising Commercially Available Activated Carbon asCompared to Device Comprising Ultrapure Synthetic Activated Carbon UnderVoltage Hold Conditions

For comparison, devices were constructed from either ultrapure syntheticactivated carbon, as disclosed herein, or a commercially availableactivated carbon Sample #6. The ultrapure synthetic activated carbon wasproduced as described below.

The ultrapure synthetic activated carbon Sample #8 was produced from anRF ultrapure polymer gel prepared according to the disclosed methods(i.e., binary solvent system comprised of water and acetic acid (75:25),resorcinol, formaldehyde, and ammonium acetate) that was freeze thawed,re-frozen on a lyophilizer shelf at about −30° C., and then dried undervacuum. The dried ultrapure polymer gel was then pyrolyzed at 850° C.under nitrogen gas followed by activation at 950° C. under CO₂ gas flow,as consistent with processes described herein. The ultrapure syntheticactivated carbon thus produced had a tap density of about 0.42 g/cm³, aspecific surface area of about 1836 m²/g, a total pore volume of about0.95 cm³/g, a fractional pore volume of about 54% for pores withdiameter of 20 nm or less relative to total pore volume, a fractionalpore volume of about 82% for pores with a diameter of 100 nm or lessrelative to total pore volume, a fractional pore surface of about 81%for pores with a diameter of 20 nm or less relative to total poresurface and a fractional pore surface area of about 97% for pores with adiameter of 100 nm or less relative to total pore surface area.

The ultrapure synthetic activated carbon Sample #9 was produced from aRF ultrapure polymer gel prepared according to the disclosed methods(i.e., binary solvent system comprised of water and acetic acid (75:25),resorcinol, formaldehyde, and ammonium acetate) that was frozen bysubmerging RF ultrapure polymer gel particles in liquid nitrogen, dryingunder vacuum, and then pyrolyzing in a rotary kiln with the temperatureacross the kiln having three hot zones set to temperatures from 650° C.,850° C. and 850° C., respectively, and the material was subjectedpyrolysis under nitrogen gas flow followed by activation at 950° C.under CO₂ gas flow, as consistent with processes described herein. Theultrapure synthetic activated carbon had a tap density of about 0.42g/cm³, a specific surface area of about 2148 m²/g, a total pore volumeof greater than about 0.93 cm³/g, a fractional pore volume of about 72%for pores with a diameter of 20 nm or less relative to total porevolume, a fractional pore volume of about greater than 99% for poreswith a diameter of 100 nm or less relative to total pore volume, afractional pore surface of about 80% for pores with a diameter of 20 nmor less relative to total pore surface, and a fractional pore surfacearea of greater than about 99% for pores with a diameter of 100 nm orless relative to total pore surface area.

The devices were subjected to a voltage hold at 2.7 V for 24 hours at 65C.°. The devices were then tested for their capacitance from a constantcurrent discharge between 2.7 and 1.89 V at current densities of 0.5A/g, 1 A/g, 4 A/g, and 8 A/g (acetonitrile solvent, TEATFB electrolyte).

The data for relative gravimetric capacitance remaining as compared tobefore the voltage hold process are presented in Table 14 (Sample #6)and Table 15 and Table 16 (for ultrapure synthetic activated carbonsamples 8 and 9, respectively). The data show a dramatic decrease in thevolumetric capacitance after the voltage hold process for thecommercially available activated carbon. In contrast, the decrease inperformance for the device containing ultrapure synthetic activatedcarbon was much lower.

TABLE 14 Capacitance Performance Parameters for Sample #6 CurrentDensity % Capacitance Before % Capacitance After Sample (A/g) VoltageHold Voltage Hold Sample #6 0.5 100% 69% 1 100% 60% 4 100% 20% 8 100%0.6% 

TABLE 15 Capacitance Performance Parameters for Ultrapure SyntheticActivated Carbon #8 Current % Capacitance Density Before % CapacitanceAfter Sample (A/g) Voltage Hold Voltage Hold Ultrapure Synthetic 0.5100% 91% Activated Carbon #8 1 100% 87% 4 100% 58% 8 100% 18%

TABLE 16 Capacitance Performance Parameters for Ultrapure SyntheticCarbon #9 Current % Capacitance Density Before % Capacitance AfterSample (A/g) Voltage Hold Voltage Hold Ultrapure Synthetic 0.5 100% 89%Activated Carbon #9 1 100% 85% 4 100% 68% 8 100% 54%

Example 26 Electrochemical Performance of Electric Double LayerCapacitor Devices Comprising Commercially Available Activated Carbon asCompared to Device Comprising Ultrapure Synthetic Activated Carbon UnderVoltage Hold Conditions

For comparison, devices were constructed from either ultrapure syntheticactivated carbon, as disclosed herein, or a commercially availableactivated carbon: Sample #6. The ultrapure synthetic activated carbonwas produced as described below.

The ultrapure synthetic activated carbon Sample #10 was produced from anRF ultrapure polymer gel, prepared according to the disclosed methods(i.e. binary solvent system comprised of water and acetic acid (75:25),resorcinol, formaldehyde, and ammonium acetate), that was frozen on alyophilizer shelf at about −50° C., and then dried under vacuum. Thedried ultrapure polymer gel was then pyrolyzed at 850° C. under nitrogengas followed by activation at 900° C. under CO₂ gas flow, as consistentwith processes described herein. The ultrapure synthetic activatedcarbon thus produced had a tap density of about 0.307 g/cm³, a specificsurface area of about 1600 m²/g, a total pore volume of about 1.02cm³/g, a fractional pore volume of about 59% for pores with diameter of2 nm or less relative to total pore volume, a fractional pore volume ofabout 76% for pores with a diameter of 10 nm or less relative to totalpore volume, a fractional pore surface area of about 94% for pores witha diameter of 2 nm or less relative to total pore surface and afractional pore surface area of about 98% for pores with a diameter of10 nm or less relative to total pore surface area.

The devices were subjected to a voltage hold at 3.5V for 25 hours atroom temperature. The devices were then tested for their capacitancefrom a constant current discharge between 3.5 and 0.1 V at constantcurrents of 1, 10, 50 mA (propylene carbonate solvent, TEATFBelectrolyte).

The data for relative volumetric capacitance remaining as compared tobefore the voltage hold process are presented in Table 17 (for Sample#6) and Table 18 (for ultrapure synthetic activated carbon Sample #10).The data show a dramatic decrease in the volumetric capacitance afterthe voltage hold process for the commercially available activatedcarbon. In contrast, the decrease in performance for the devicecontaining ultrapure synthetic activated carbon was much lower.

TABLE 17 Capacitance Performance Parameters for Sample #6 DischargeCurrent % Capacitance % Capacitance After Sample (mA) Before VoltageHold Voltage Hold Sample #6 1 100% 59% 10 100% 63% 50 100% 3%

TABLE 18 Capacitance Performance Parameters for Ultrapure SyntheticActivated Carbon Sample #10 Discharge % Capacitance Current BeforeVoltage % Capacitance After Sample (mA) Hold Voltage Hold UltrapureSynthetic 1 100% 101% Activated Carbon 10 100% 72% #10 50 100% 59%

Example 27 Electrochemical Performance of Electric Double LayerCapacitor Devices Comprising Commercially Available Activated Carbon asCompared to Device Comprising Ultrapure Synthetic Activated Carbon UnderCycling Conditions

For comparison, devices were constructed from ultrapure syntheticactivated carbon materials as disclosed herein or a commerciallyavailable activated carbon: Sample #6. The gravimetric and volumetricpower and gravimetric and volumetric energy performance data for thesecommercially available carbons are presented in Table 13 for dischargebetween 2.7 and 1.89V. The ultrapure synthetic activated carbon wasproduced as described below.

The ultrapure synthetic activated carbon Sample #11 was produced from anRF ultrapure polymer gel, prepared according to the disclosed methods(i.e., binary solvent system comprised of water and acetic acid (75:25),resorcinol, formaldehyde, and ammonium acetate), that was ground intoparticles, frozen on a lyophilizer shelf at about −30° C., dried undervacuum, and then pyrolyzed at 850° C. under nitrogen gas followed byactivation at 900° C. under CO² gas flow, as consistent with processesdescribed herein. The ultrapure synthetic activated carbon had a tapdensity of about 0.28 g/cm³, a specific surface area of about 1754 m²/g,a total pore volume of about 1.15 cm³/g, a fractional pore volume ofabout 53% for pores with a diameter of 20 nm or less relative to totalpore volume, a fractional pore volume of about 76% for pores with adiameter of 100 nm or less relative to total pore volume, a fractionalpore surface of about 91% for pores with a diameter of 20 nm or lessrelative to total pore surface and a fractional pore surface area ofabout 99% for pores with a diameter of 100 nm or less relative to totalpore surface area.

The devices were subjected to several thousand cycling events between 2V and 1 V (acetonitrile solvent, TEATFB electrolyte). The datademonstrate that the ultrapure synthetic activated carbon Sample #11 asdisclosed herein retains 99.78% of it's original capacitance after 3000cycles. The data demonstrates that Sample #6 electrode prepared inexactly the same way has retained only 97.11% of its originalcapacitance after 2600 cycles. The degradation from 100% to 99.78% isalmost perfectly linear in both cases and so if it is extrapolated outto 10,000 cycles, the ultrapure carbon would retain 99.25% of it'soriginal capacitance and the Sample #8 capacitor would retain only88.89% of it's original capacitance. This indicates that the ultrapuresynthetic carbon is substantially more stable in the first severalthousand cycles as opposed to Sample #6 (Cycling data at 4 A/g between2V and 1V in ACN). As can be seen, the ultrapure synthetic carbonexhibits a dramatically improved retention of capacitance after cyclingcompared to non-ultrapure carbons.

Example 28 Preparation of Dried Ultrapure Polymer Gel

According to the methods disclosed herein a ultrapure polymer gel wasprepared from a binary solvent system comprised of water and acetic acid(75:25), resorcinol, formaldehyde, and ammonium acetate. The materialwas then placed at elevated temperature to allow for gellation to createan ultrapure polymer gel. Ultrapure polymer gel particles were createdfrom the ultrapure polymer gel and passed through a Stedman Auroracrusher outfitted with corrosion resistant stainless steel blades and ⅝″screen. Ultrapure polymer gel particles were frozen by immersion inliquid nitrogen, and loaded into a lyophilization tray at a loading of 3to 7 g/in², and lyophilized. The time to dry (as inferred from time forproduct to reach within 2° C. of shelf temperature) was related to theproduct loading on the lyophilizer shelf.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a Micromeritics Surface Area and Porosity Analyzer (modelTriStar II). The measured specific surface area using the BET approachwas in the range of about 500 to 700 m²/g.

Example 29 Production of Ultrapure Pyrolyzed Synthetic Carbon Materialfrom Dried Ultrapure Polymer Gel

The dried gel as described in Example 28 was pyrolyzed by passagethrough a rotary kiln (metal tube with mullite liner with 4.18 inchinner diameter) at 0.7 kg/h at 680 to 850° C. gradient hot-zones with anitrogen gas flow of 4,250 L/h rate. The weight loss upon pyrolysis wasabout 50% to 52%.

The surface area of the pyrolyzed dried ultrapure polymer gel wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the standard BETapproach was in the range of about 600 to 700 m²/g.

Example 30 Preparation of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 29 wasactivated by incubation at 900° C. in a quartz tube (3.75 inch innerdiameter) with 6.7 L/min CO₂ flow rate, to achieve a final weight loss(compared to the starting pyrolyzed carbon) of about 55%.

The surface area of the activated carbon material was examined bynitrogen surface analysis using a surface area and porosity analyzer.The measured specific surface area using the BET approach was in therange of about 2500 m²/g. The measured pore volume (Dv50) of theultrapure synthetic activated carbon was at a pore size of about 1.8 nm.The measured pore volume (Dv5) of the ultrapure synthetic activatedcarbon was at a pore size of about 0.5 nm. The measured total porevolume of the ultrapure synthetic activated carbon was 1.07 cc/g.

Example 31 Electric Double Layer Capacitor Device Comprising UltrapureSynthetic Activated Carbon

The ultrapure synthetic activated carbon of Example 30 was used as anelectrode material for an electric double later capacitor device asdescribed below.

Capacitor electrodes comprised 97 parts by weight carbon particles(average particle size 5-15 microns) and 3 parts by weight Teflon. Thecarbon and Teflon were masticated in a mortar and pestle until theTeflon was well distributed and the composite had some physicalintegrity. After mixing, the composite was rolled out into a flat sheet,approximately 50 microns thick. Electrode disks, approximately 1.59 cmin diameter, were punched out of the sheet. The electrodes were placedin a vacuum oven attached to a dry box and heated for 12 hours at 195°C. This removed water adsorbed from the atmosphere during electrodepreparation. After drying, the electrodes were allowed to cool to roomtemperature, the atmosphere in the oven was filled with argon and theelectrodes were moved into the dry box where the capacitors were made.

Standard 2325 stainless steel coin cell parts were used in coin cellassembly. A 0.625 inch diameter carbon coated aluminum disk was used asa contact resistance reducer in the positive cap. A 0.625 inch diametercarbon electrode on top of the aluminum disk was saturated with severaldrops of electrolyte comprising 1.0 M tetraethylene ammoniumtetrafluoroborate in acetonitrile. Two pieces of cellulose based porousseparator with 0.825 inch from NKK, Inc were then placed on top of thecarbon disk. Next, the second piece of carbon electrode was placed onthe separator and one more drop of electrolyte was added to wet the topsurface. After that the second carbon coated aluminum contact resistancereducer was put on the electrode. Then one stainless spacer and springwas placed sequentially and the whole stack was covered in the negativecap with a polypropylene grommet. The whole cell stack was then put ontoa hydraulic pressure operated crimper and crimped for 1 minute at fullpressure to form a sealed coin cell.

Example 32 Electrochemical Performance of an Electric Double LayerCapacitor Device Comprising Ultrapure Synthetic Activated Carbon

The device described in Example 31 was subjected to electrical testingwith a potentiostat/function generator/frequency response analyzer.Capacitance was measured by a constant current discharge method,comprising applying a current pulse for a known duration and measuringthe resulting voltage profile over time. By choosing a given time andending voltage, the capacitance was calculated from the followingC=It/ΔV, where C=capacitance, I=current, t=time to reached the desiredvoltage and ΔV=the voltage difference between the initial and finalvoltages. The specific capacitance based on the weight and volume of thetwo carbon electrodes was obtained by dividing the capacitance by theweight and volume respectively. This data is reported in Table 19 fordischarge between 2.7 and 1.89V.

TABLE 19 Capacitance Performance Parameters of an EDLC ComprisingUltrapure Synthetic Activated Carbon Capacitance Performance ParametersMeasured Value Gravimetric Power* 16.9 W/g Volumetric Power* 11.7 W/ccGravimetric Energy* 20.6 Wh/kg Volumetric Energy* 14.3 Wh/literGravimetric Capacitance @ 0.5 A/g 30.5 F/g Volumetric Capacitance @ 0.5A/g 21.4 F/cc Gravimetric Capacitance @ 1.0 A/g 29.6 F/g VolumetricCapacitance @ 1.0 A/g 20.8 F/cc Gravimetric Capacitance @ 4.0 A/g 24.6F/g Volumetric Capacitance @ 4.0 A/g 17.2 F/cc Gravimetric Capacitance @8.0 A/g 18.7 F/g Volumetric Capacitance @ 8.0 A/g 13.1 F/cc *Byconstantcurrent discharge from 2.7 to 1.89 volts with TEATFB in AN.

Example 33 Preparation of Dried Ultrapure Polymer Gel

According to the methods disclosed herein an ultrapure polymer gel wasprepared from a binary solvent system comprised of water and acetic acid(75:25), resorcinol, formaldehyde, and ammonium acetate. The materialwas then placed at elevated temperature to allow for gellation to createa ultrapure polymer gel. Ultrapure polymer gel particles were createdfrom the ultrapure polymer gel and passed through 4750 micron meshsieve, and said ultrapure polymer gel particles were loaded into alyophilization tray at a loading of 3 to 7 g/in², frozen on alyophilizer shelf which was pre-cooled to about −40° C., andlyophilized. The time to dry (as inferred from time for product to reachwithin 2° C. of shelf temperature) was related to the product loading onthe lyophilizer shelf.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a Micromeritics Surface Area and Porosity Analyzer (modelTriStar II). The measured specific surface area using the BET approachwas in the range of about 500 to 600 m²/g.

Example 34 Production of Ultrapure Pyrolyzed Synthetic Carbon Materialfrom Dried Ultrapure Polymer Gel

The dried gel as described in Example 11 was pyrolyzed by passagethrough a rotary kiln (quartz tube with 3.75 in inner diameter) at 850°C. with a nitrogen gas flow of 200 L/h rate. The weight loss uponpyrolysis was about 52%.

The surface area of the pyrolyzed dried ultrapure polymer gel wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the standard BETapproach was in the range of about 500 to 700 m²/g.

Example 35 Production of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 12 wasactivated in a batch process process through a rotary kiln (quartz tubewith 3.75 in inner diameter) at 900° C. under a CO₂ flow rate of 400L/h, resulting in a total weight loss of about 45%.

The surface area of the ultrapure synthetic activated carbon wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the BET approach wasin the range of about 1600 to 2000 m²/g. This carbon will be referred toherein as Sample 4.

Example 36 Preparation of Dried Ultrapure Polymer Gel

According to the methods disclosed herein a ultrapure polymer gel wasprepared from a binary solvent system comprised of water and acetic acid(75:25), resorcinol, formaldehyde, and ammonium acetate. The materialwas then placed at elevated temperature to allow for gellation to createa ultrapure polymer gel. Ultrapure polymer gel particles were createdfrom the ultrapure polymer gel and passed through 4750 micron meshsieve, and said ultrapure polymer gel particles were loaded into alyophilization tray at a loading of 3 to 7 g/in², frozen on alyophilizer shelf which was pre-cooled to about −40 C, and lyophilized.The time to dry (as inferred from time for product to reach within 2° C.of shelf temperature) was related to the product loading on thelyophilizer shelf.

The surface area of the dried gel was examined by nitrogen surfaceanalysis using a Micromeritics Surface Area and Porosity Analyzer (modelTriStar II). The measured specific surface area using the BET approachwas in the range of about 500 to 700 m²/g.

Example 37 Production of Ultrapure Pyrolyzed Synthetic Carbon Materialfrom Dried Ultrapure Polymer Gel

The dried gel as described in Example 11 was pyrolyzed by passagethrough a rotary kiln (quartz tube with 3.75 in inner diameter) at 850°C. with a nitrogen gas flow of 200 L/h rate. The weight loss uponpyrolysis was about 52%.

The surface area of the pyrolyzed dried ultrapure polymer gel wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the standard BETapproach was in the range of about 500 to 700 m²/g.

Example 38 Production of Ultrapure Synthetic Activated Carbon

The pyrolyzed synthetic carbon material as described in Example 12 wasactivated in a batch process through a rotary kiln (quartz tube with3.75 in inner diameter) at 900° C. under a CO₂ flow rate of 400 L/h,resulting in a total weight loss of about 44%.

The surface area of the ultrapure synthetic activated carbon wasexamined by nitrogen surface analysis using a surface area and porosityanalyzer. The measured specific surface area using the BET approach wasin the range of about 1600 to 2000 m²/g. This carbon will be referred toherein as Sample 5.

Example 39 Measurement of H, N, O for Ultrapure Synthetic ActivatedCarbon

The synthetic activated carbon material identified as Sample 1 wasanalyzed for H, N and O at Elemental Analysis, Inc. (Lexington, Ky.).The data showed that the hydrogen content was 0.25%, the nitrogencontent was 0.21%, and the oxygen content was 0.53%.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet, areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments. These and other changes can be made to the embodiments inlight of the above-detailed description. In general, in the followingclaims, the terms used should not be construed to limit the claims tothe specific embodiments disclosed in the specification and the claims,but should be construed to include all possible embodiments along withthe full scope of equivalents to which such claims are entitled.Accordingly, the claims are not limited by the disclosure.

The invention claimed is:
 1. An ultrapure synthetic carbon materialcomprising a BET specific surface area of at least 1500 m²/g and a totalimpurity content of less than 500 ppm of elements having atomic numbersranging from 11 to 92 as measured by proton induced x-ray emission. 2.The carbon material of claim 1, wherein the carbon material is anultrapure synthetic amorphous carbon material.
 3. The carbon material ofclaim 1, wherein the carbon material comprises a total impurity contentof less than 200 ppm of elements having atomic numbers ranging from 11to 92 as measured by proton induced x-ray emission.
 4. The carbonmaterial of claim 1, wherein the ash content of the carbon material isless than 0.03% as calculated from proton induced x-ray emission data.5. The carbon material of claim 1, wherein the ash content of the carbonmaterial is less than 0.01% as calculated from proton induced x-rayemission data.
 6. The carbon material of claim 1, wherein the carbonmaterial comprises at least 95% carbon by weight as measured bycombustion analysis and proton induced x-ray emission.
 7. The carbonmaterial of claim 1, wherein the carbon material comprises less than 3ppm iron as measured by proton induced x-ray emission.
 8. The carbonmaterial of claim 1, wherein the carbon material comprises less than 1ppm nickel as measured by proton induced x-ray emission.
 9. The carbonmaterial of claim 1, wherein the carbon material comprises less than 5ppm sulfur as measured by proton induced x-ray emission.
 10. The carbonmaterial of claim 1, wherein the carbon material comprises less than 1ppm chromium as measured by proton induced x-ray emission.
 11. Thecarbon material of claim 1, wherein the carbon material comprises lessthan 1 ppm copper as measured by proton induced x-ray emission.
 12. Thecarbon material of claim 1, wherein the carbon material comprises lessthan 100 ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur,less than 100 ppm calcium, less than 20 ppm iron, less than 10 ppmnickel, less than 140 ppm copper, less than 5 ppm chromium and less than5 ppm zinc as measured by proton induced x-ray emission.
 13. The carbonmaterial of claim 1, wherein the carbon material comprises less than 50ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, less than10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, less than1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc asmeasured by proton induced x-ray emission.
 14. The carbon material ofclaim 1, wherein the carbon material comprises less than 3.0% oxygen,less than 0.1% nitrogen and less than 0.5% hydrogen as determined bycombustion analysis.
 15. The carbon material of claim 1, wherein thecarbon material comprises less than 1.0% oxygen as determined bycombustion analysis.
 16. The carbon material of claim 1, wherein thecarbon material comprises a pyrolyzed ultrapure polymer cryogel.
 17. Thecarbon material of claim 1, wherein the carbon material comprises anactivated ultrapure polymer cryogel.
 18. The carbon material of claim 1,wherein the carbon material comprises a pore volume of at least 0.7cc/g.
 19. The carbon material of claim 1, wherein the carbon materialcomprises a BET specific surface area of at least 2000 m²/g.
 20. Thecarbon material of claim 1, wherein the carbon material comprises a BETspecific surface area of at least 2400 m²/g.
 21. A device comprising anultrapure synthetic carbon material, wherein the ultrapure syntheticcarbon material comprises a BET specific surface area of at least 1500m²/g and a total impurity content of less than 500 ppm of elementshaving atomic numbers ranging from 11 to 92 as measured by protoninduced x-ray emission.
 22. The device of claim 21, wherein the carbonmaterial is an ultrapure synthetic amorphous carbon material.
 23. Thedevice of claim 21, wherein the device is a battery.
 24. The device ofclaim 23, wherein the device is a lithium/carbon battery, zinc/carbon,lithium air battery or lead acid battery.
 25. The device of claim 21,wherein the device is an electric double layer capacitor (EDLC) devicecomprising: a) a positive electrode and a negative electrode whereineach of the positive and the negative electrodes comprise the ultrapuresynthetic carbon material; b) an inert porous separator; and c) anelectrolyte; wherein the positive electrode and the negative electrodeare separated by the inert porous separator.
 26. The device of claim 25,wherein the EDLC device comprises a gravimetric power of at least 15W/g.
 27. The device of claim 25, wherein the EDLC device comprises avolumetric power of at least 10 W/cc.
 28. The device of claim 25,wherein the EDLC device comprises a gravimetric energy of at least 20.0Wh/kg.
 29. The device of claim 25, wherein the EDLC device comprises avolumetric energy of at least 10.0 Wh/liter.
 30. The device of claim 25,wherein the EDLC device comprises a gravimetric capacitance of at least25 F/g as measured by constant current discharge from 2.7 V to 0.1 Vwith a 5 second time constant employing a 1.8 M solution oftetraethylammonium-tetrafluoroborate in acetonitrile electrolyte and acurrent density of 0.5 A/g.
 31. The device of claim 25, wherein the EDLCdevice comprises a volumetric capacitance of at least 20 F/cc asmeasured by constant current discharge from 2.7 V to 0.1 V with a 5second time constant employing a 1.8 M solution oftetraethylammonium-tetrafluoroborate in acetonitrile electrolyte and acurrent density of 0.5 A/g.
 32. The device of claim 25, wherein thecarbon material comprises a total impurity content of less than 200 ppmof elements having atomic numbers ranging from 11 to 92 as measured byproton induced x-ray emission.
 33. The device of claim 25, wherein theash content of the carbon material is less than 0.03% as calculated fromproton induced x-ray emission data.
 34. The device of claim 25, whereinthe ash content of the carbon material is less than 0.01% as calculatedfrom proton induced x-ray emission data.
 35. The device of claim 25,wherein the carbon material comprises at least 95% carbon as measured bycombustion analysis and proton induced x-ray emission.
 36. The device ofclaim 25, wherein the carbon material comprises less than 3 ppm iron asmeasured by proton induced x-ray emission.
 37. The device of claim 25,wherein the carbon material comprises less than 1 ppm nickel as measuredby proton induced x-ray emission.
 38. The device of claim 25, whereinthe carbon material comprises less than 5 ppm sulfur as measured byproton induced x-ray emission.
 39. The device of claim 25, wherein thecarbon material comprises less than 1 ppm chromium as measured by protoninduced x-ray emission.
 40. The device of claim 25, wherein the carbonmaterial comprises less than 1 ppm copper as measured by proton inducedx-ray emission.
 41. The device of claim 25, wherein the carbon materialcomprises less than 100 ppm sodium, less than 300 ppm silicon, less than100 ppm calcium, less than 50 ppm sulfur, less than 20 ppm iron, lessthan 10 ppm nickel, less than 140 ppm copper, less than 5 ppm chromiumand less than 5 ppm zinc as measured by proton induced x-ray emission.42. The device of claim 25, wherein the carbon material comprises anactivated ultrapure polymer cryogel.
 43. The device of claim 25, whereinthe carbon material comprises a BET specific surface area of at least2000 m²/g.
 44. The device of claim 25, wherein the carbon materialcomprises a BET specific surface area of at least 2400 m²/g.
 45. Anelectrode comprising an ultrapure synthetic carbon material and abinder, wherein the ultrapure synthetic carbon material comprises a BETspecific surface area of at least 1500 m²/g and a total impurity contentof less than 500 ppm of elements having atomic numbers ranging from 11to 92 as measured by proton induced x-ray emission.
 46. The electrode ofclaim 45, wherein the carbon material is an ultrapure syntheticamorphous carbon material.